Methods and compositions for preparing consumables with optical shifting properties

ABSTRACT

Ingestible compositions comprising a chromic change agent together with methods of making and using them are provided. The chromic change agent alternatively may be associated with the ingestible, such as a packaging material for the ingestible. In response to a triggering event, physical or chemical, the chromic change agent changes color to provide information as to the history of the ingestible, either prior or contemporaneous with use. Depending on the use, the color change agent may be reversible or irreversible. Various solid or liquid ingestible compositions are provided for determining ingestible temperature, storage temperature, user temperature, light exposure, pH change, hydration or solvation change, mechanical stress, and the like, particularly in comestibles. Of particular interest are polydiacetylene polymers that may be formulated to provide compositions having numerous different color transition triggering mechanisms. The invention is also related to other chromic change agents that may be incorporated into ingestibles.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation in part of U.S. Ser. No.09/892,018 filed Jun. 25, 2001 which is a continuation in part of U.S.Ser. No. 09/602,001 filed Jun. 23, 2000, which disclosures are herebyincorporated by reference.

INTRODUCTION

[0002] 1. Technical Field

[0003] The field of this invention is methods and compositions forpreparing an edible consumable or ingestible comprising one or morechromic change agent that is safe for human or animal consumption thatinteractively modulates a color transition in the edible consumable oringestible.

[0004] 2. Background

[0005] Foods, beverages, medications and a variety of edible productswith intrinsic color change properties can find a multitude of uses formanufacturers and consumers alike. They can be developed and marketedfor entertainment purposes, such as graphics on the surface of food thatchange color, giving rise to a visual effect that is both pleasing andinteresting for children. A variety of new food categories can beproduced to contain the chromic material. Food producers are in need ofnew means to differentiate brands, extend product lines, advertise andpromote, and create new product lines. Generally, food developers arelimited to new flavors, colors, presentations, packaging, andcombinations for product differentiation. Entirely new categories offoods, beverages, and medications can be created by introducing a newintrinsic property during processing.

[0006] Color changes may release or expose hidden messages which can beused for promotional or marketing purposes. Color changes can visuallysignal the consumer when the food is “done” to a satisfactory extent andsafe to eat, or that the food is still in the process of being cooked.Color changes can be used to communicate optically with a cookinginstrument telling the cooking instrument the level of doneness througha bar code change.

[0007] Color change foods can indicate to consumers or institutions thatthe food offered is sterile due to its color at purchase. Subsequentchanges in color could indicate that the food has become stale orspoiled. Safe food storage temperatures can be indicated by the food orbeverage directly where a color change indicates that the food was heldat an inappropriate temperature for a period of time. The color changecan be used to signal the timely release of a certain nutrient or flavorinto the food. The chromic change can also be used to communicate thenature of food to be consumed. For example, chromic change agents cantell the consumer how “hot” a hot sauce really is, the fat content ofcertain foods, the level of carbonation in soft drinks, or the level ofa biological or chemical in a food, such as caffeine or allergens.

[0008] Certain spices and other foods should be irradiated withhigh-energy sources to ensure that potential microbial contamination hasbeen eliminated, thereby protecting the consumer. Foods containing achromic agent that changes color upon irradiation can communicate to theconsumer or the food processor that proper irradiation has taken place.

RELEVANT REFERENCES

[0009] Colored food products on the market today involve the use ofcommercialized dyes combined with a capsule of waxes or other opaquematrices that mask the underlying dye. The dye molecules become visuallyexposed upon dissolving or melting of the encapsulating material. Anexample of releasing a dye into hot water involves Quaker Oat's DeepBlue Hot Oatmeal. An example of dissolving a coated dye into cold milkinvolves a version Nabisco's Oreo Cookie that releases a blue dye intomilk when the cookie is dipped into the milk. An example using meltingwaxes to reveal an underlying color involves Kellogg's PopTarts where awhite wax is coated over a colored sprinkle. When the pastry is heatedthe wax melts to reveal the color. An example of beverage additive isKraft Food's Kool-Aid Magic Twists incorporating an entrapped dye thatbecomes revealed as the coating on the food color is dissolved. Anexample of a color change when a food product is eaten is FritoLay'sCheeto's Cheese Puffs, which release a dye into one's mouth when theproduct is wetted and chewed. An example of a chewing gum which turnsone's mouth blue is Blue Mouth Chewing Gum from Creative ProductsManufacturing. In each case a color is revealed by releasing or exposinga hidden dye and not an intrinsic chromic change that results from amolecular change in the chromic change agent itself.

[0010] References of interest include U.S. Pat. Nos. 4,859,538;5,144,112; 5,156,810; 5,189,281; 5,273,360; 5,415,999; 5,685,641;5,788,375; 5,918,981; and 6,046,455.

SUMMARY OF THE INVENTION

[0011] Environmentally responsive components are intrinsicallyassociated with ingestibles, such as foods, beverages and medicaments,to be consumed as part of the ingestible, while providing knowledge ofan informative or entertaining character. Specifically, physiologicallyacceptable chromic materials, e.g. polymerized polyacetylenes, areassociated with the ingestible so as to be consumed by the user. Thechromic material changes color in response to various environmentalclues, such as temperature, pH, radiation, and physical stress, amongothers.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS

[0012] Ingestibles are provided comprising a chromic material thatchanges color in response to environmental cues.

[0013] A variety of color change triggering processes can be used tocause the color change of chromic change agents depending on the type ofchemistry involved, such as temperature, pH changes, changes in ionicstrength, mechanical changes such as stress or pressure during mixing orcontortion, chemical changes such as the addition of a second component,exposure to light for a photochromic effect, biochemical reactions suchas binding pair interaction (e.g., an antibody-antigen interaction, areceptor-ligand interaction), solvent environment changes, hydration ordehydration, solvent changes, and enzymatic changes where enzymes in thefood can induce a change. The color-indicating material can be processeddirectly into the ingestible, coated on the surface, released in atimely manner, or be made to be exposed through a discrete color changetriggering process.

[0014] By ingestibles is intended compositions that are taken orally,even though they may not be digested. Therefore, ingestibles includefoods, medicaments, toothpaste, mouth washes, gargles, swabs, and thelike, where the food is introduced into the mouth and may then berejected or may reside in the mouth for a limited period of time. Sincefoods are the primary application of the subject invention, foods arediscussed as illustrative of ingestibles generally. The chromicmaterials are physiologically acceptable, particularly polymerizedpolyacetylenes, which can be incorporated with the ingestible during orafter processing. Only a small amount of the chromic material need beincorporated, where the chromic material may be suffused through theingestible, partially penetrate the ingestible or primarily be anadherent coating on the ingestible. The ingestible is porous or liquid,so that the chromic composition, by itself or in conjunction with anedible carrier, interpenetrates the ingestible, where the penetrationmay be throughout the ingestible, a limited depth into the ingestible,or into the surface to provide an adherent surface.

[0015] Polydiacetylenes as a class of ingestible chromic agents offerseveral advantages since they exhibit a broad range of beneficialcharacteristics. They have a large extinction coefficient showing a highcolor contrast, so that proportionally less chromic change material maybe required to achieve an optical effect than materials such asentrapped dyes. Polydiacetylenes are organic and can be modified tocreate a wide range of permutations applicable to different chromictriggering mechanisms, ingestible applications, and processing methods.They can be structurally modified to have more than one intrinsic colorchange (e.g. blue—magenta—red or blue red—yellow). They can be modifiedto be compatible with the different food matrices (e.g., fats, aqueous,starch, protein, inorganic salts, sugars or the like). They can be madestructurally inert such that they are odorless and tasteless, thus notaffecting the foods to which they are added. The polymer form is a highmolecular weight structure thereby, reducing its potential foradsorption during the digestion process. Polydiacetylenes are compatiblewith a variety of compositions used in the food industry for coatingsand processing, making them amenable to existing processing methodswithout complete processing line redesign (e.g., solid food forms orliquid food forms). They can be made into stable forms making them goodcandidates for tolerating the stresses of production, shipping andstorage.

[0016] Polydiacetylenic and other chromic change materials that undergoan intrinsic color change respond directly to a triggering event ratherthan simply releasing a color. A direct response chromic change has thesignificant advantage that the chromic agent itself can be engineeredand designed to meet a broad and varied interest in the food,pharmaceutical and other relevant industries. In the case ofpolydiacetylenic materials, the chromic agent can be chemically enhancedwith different substituents and functional groups for variousapplications while maintaining the intrinsic color changecharacteristics. The unique conformational change mechanism thatpolydiacetylenes undergo during a color-changing triggering eventprovides a unique means to match the material with food-basedchemistries, food processing methods, and printing and applicationprocesses.

[0017] Since polydiacetylenic materials can be modified to change colorto a variety of different optical triggering mechanisms, they have theadditional advantage that they may serve as indicators or reporters fora variety of different monitoring processes of interest to the food andpharmaceutical industries and consumers. Examples of such monitoringprocesses include cooking temperatures, presence of toxic chemical ormicrobial contaminants, heavy metal, the presence of carcinogens,allergens that can cause an immediate deadly reaction if the food isconsumed, food content (e.g. specific substances in food which caninduce a color change event if present), DNA or RNA, various geneproducts or genetically engineered substances, food oxidation state,freshness, temperatures that the food may have been raised to duringshipping and handling, whether certain foods have been irradiatedaccording to specific guidelines, and the like.

[0018] Diacetylenic and polydiacetylenic compounds may be produced in amultitude of forms or substituents for compatibility and functionalitywith foods, beverages and medications. The diacetylenic group may bemodified with lipid-like groups for solid phase or liquid phasecompatibility, carbohydrates, sugars, polar and apolar groups,functional groups such as amines, carboxylic acids, alcoholic groups,esters, amides, charge complexes, aliphatic groups, ethers, polyethers,amino acids, proteins, nucleic acids, mesogenic side chains, sulfhydrylgroups, block co-polymers and other groups which may be used to createspecifically desired characteristics. Compositions may be preparedhaving up to about 20 weight % of the polydiacetylenic polymer forcoating, which compositions further comprise carbohydrates, lipids orother physiologically acceptable composition.

[0019] The diacetylenic compounds or chromic agents present, whethermonomers or polymers, in the composition added to the ingestible willgenerally be present in at least 1 weight %, more usually at least about5 weight %, and may be 75 weight % or more, usually being not more thanabout 60 weight %.

[0020] Diacetylenic monomer chemistries: Classes of photochromic,thermochromic, hydrochromic, lipochromic, and physiochromic polymers canbe made from a variety of organic diacetylenic monomers including shortchain molecules with no side chains or substituents, short chainmolecules containing one or more functional groups and aliphaticmonomers that vary in length from 10 carbon units to 50 or more carbonunits with or without various functional side chains or substituents.Molecules can be hydrophobic or hydrophilic depending on the desiredapplication. They can be neutral or charged in order to create a desiredintermolecular or intramolecular effect. The molecule can be non-polar,mono-polar, or multi-polar. Diacetylenic monomers can be symmetric orasymmetric. For food grade applications, the monomer and subsequentpolymer molecules can contain food compatible groups including sugars,lipid chains, carbohydrate moieties, amino acids, peptides, proteins,complex proteins, effector groups, esters, alcoholic groups, amides,carboxamides, dextrans, heterocyclic substituents, acids, lipids,detachable nutrient groups, such as vitamins and nutraceuticals,catalytic groups such as enzymes, chelating groups, nucleotides, foodcolors, emulsifier groups, or the like.

[0021] Side chains and substituents may be chemically modified for usewith a variety of different foods. The hydrophobic or hydrophilic natureof the chemical compound can be adjusted to create compositions more orless compatible with fatty foods, carbohydrate-based foods, meats, dryfoods, cereals, baked goods or the like.

[0022] The diacetylenic monomer will be a lipid mono- or dicarboxylicnon-oxo carbonyl monomer or derivative thereof, so that acid, esters, oramides may be employed, a mono- or diol, ether or ester thereof, wherethe acid may be organic or inorganic, e.g. phosphate, an amino orderivative thereof, where the derivative may be an organic substituentsuch as an acyl group, an aliphatic group, an aromatic group, aheterocyclic group, etc. The substituents at the termini will have from0 to 30, more usually 0 to 20 atoms, which will usually be carbon,oxygen, nitrogen, sulfur and phosphorous. The acid portion of themolecule (or underivatized portion) will generally range from 5-30, moreusually 12-30, carbon atoms and the diacetylene groups which will be inconjugation, may be situated symmetrically or asymmetrically in themolecule. Thus, the flanking alkylene groups may be the same ordifferent in a molecule, where the temperature transition of the polymerwill depend upon the chain length of the monomer, whether thediacetylene groups are symmetrical or asymmetrical, and the degree ofdifference between the length of the flanking regions, whether one usesa single monomer to form a homopolymer or two or more monomers, usuallynot more than four monomers, to form a co-polymer, and whether thechains are substituted or unsubstituted, as well as the nature anddegree of substitution. Particularly, halogen substituents, e.g.fluorine, chlorine and bromine, may be present to enhance the uppertemperature limits possible with the subject compositions, ranging froma single substituent to persubstituted. The temperature range which isattainable using the various diacetylene monomers will range from about25-300° C., usually not exceeding 200° C., more usually from about25-200° C. For the purposes of this invention, the range of interestwill be from about 30-200° C., more usually from about 35-200° C., andparticularly from about 35-150° C.

[0023] For the most part, the diacetylene monomers will have thefollowing formula:

R(CH₂)_(n)(C≡C)₂(CH₂)_(m)Y  (1)

[0024] wherein:

[0025] Y is COX¹, amino (including substituted amino, e.g. alkylsubstituted amino of from about 1-6 carbon atoms), oxy having from 0 to6 carbon atoms, thio of from 0 to 6 carbon atoms, cyano, halo, etc.;

[0026] m and n are at least 1 and total 8-25, preferably n is at least2, more preferably both m and n are at least 2;

[0027] R is H or Y; and

[0028] X and X′ may be the same or different, usually the same, may beany of the groups indicated above, generally being H, OH, OT, where T isof from 1-8, usually 1-6 carbon atoms having from 0-(n-2) substituents,wherein n is the number of carbon atoms and the substituent may be oxy,amino, halo, thiol ,etc, usually aliphatic, e.g. hydroxyalkyl, andaminoalkyl; or NT¹, T², wherein T¹ and T² are the same or different,usually the same and will have from 1-8, usually 1-6 carbon atoms, thetotal number of carbon atoms of T¹ and T² usually not being greater thanabout 6 and each having from 0-(n-2) substituents as described above,particularly oxy, one of T¹ and T² may be unsubstituted or substitutedamino (hydrazino), where the substituents will come within thedefinition of T¹, polyalkyleneoxy, wherein alkylene is of from 2 to 3carbon atoms and may have from 2 to 50 units; or two Y's may be takentogether to form a divalent linking group of from about 2 to 2,000daltons, which will usually be 2 T's taken together (T's include T andT¹). Monomers can be used individually and in pure form. The position ofthe acetylenic groups may be symmetrical or asymmetrical in themolecule.

[0029] Of particular interest are monomers, such as 10,12-tricosadiynoicacid (C23) or 10,12-pentacosadiynoic acid (C25), which can be usedindependently during processing and production to achieve a lowersensitivity to ultraviolet irradiation (254 nm) or either compound maybe added in a percentage to the other to sensitize the mixture to makethe mixture far more sensitive to ultraviolet irradiation. 0.01-50% byweight of C25 can be added to C23 to make a mixture that polymerizes 50%or more quickly and achieves a much darker blue appearance afterpolymerization. More usually, 0.1 to 30% C25 is added to C23. Typically,1 to 20% C25 is added to C23. Formulation variations along withultraviolet irradiation times can be used to create differentthermochromic temperature settings. Combinations of formulations can beused to achieve a variety of visual effects upon temperature triggeringincluding patterns such as text, characters, images, symbols,trademarks, brand identity marks, messages, icons, logos, artisticdesigns or decorative designs. Patterns may appear to changenon-uniformly to create visual imagery such as the appearance ofmovement in a stationary picture.

[0030] The general structure of a diacetylenic monomer that ispolymerized to become a polydiacetylenic chromic change agent consistsof a diacetylenic unit with appending side chains on each end of thediacetylenic unit

A(CH ₂)n—≡—≡—(CH ₂)mB  (2)

[0031] The corresponding polydiacetylenic unit capable of undergoing achromic change is a continuous ene-yne structure with A(CH₂)n and(CH₂)mB each as side chains attached to an individual ene-yne unit:

[0032] where Z represents the number of repeating units along thepolydiacetylene backbone. Z can range in number from 2 to greater than100,000. Usually Z will vary from 5 to 10,000. Typically Z will bebetween 10 and 1,000 units.

[0033] The number of methylene units n and m may be increased ordecreased depending on the application of interest. Increasing thenumber of methylene units can have dramatically different effects on theresulting chromic triggering mechanisms. Altering the substituents A andB can have the effect of sensitizing, tuning or optimizing a particularchromic triggering mechanism in the chromic change agent. The compositestructural features of an ingestible chromic change agent can be relatedto both the chromic change mechanism as well as the degree ofresponsiveness or non-responsiveness of the agent to a triggering event.Illustrative examples of chromic agent color change mechanisms andenabling structural features are summarized below but are not intendedto limit the scope of possible mechanisms or structural permutations.

[0034] Photochromic agent color changes: The primary enabling featurefor a diacetylenic material to be photopolymerizable such that exposureto ultraviolet light (254 nm) results in the formation of a colorformation is the ordered crystal packing state of the monomericdiacetylenic unit. A, B n, and m must be balanced such that diacetylenecrystals are aligned and can be topochemically polymerized. Typically Aand B should be of a molecular size and structure to promote and notinhibit crystal packing or sterically restrict the diacetylenic unitsfrom packing close enough to each other in a crystal lattice as torestrict ene-yne bond formation to occur between units. A and B can besimilar or dissimilar in structure. A and n can be paired to comprise analkyl chain and give the molecule favorable hydrophobic-hydrophobicinteractions for inducing good crystal packing. B and m can comprise anidentical alkyl chain to A and n to give the photochrome a wax-likecharacteristic. In contrast, m can be between 1 to 20 units while B canbe a simple hydrophilic head group such as an alcohol or amine. B can bemore complex such as a carboxylic acid or amide linkage. Amine, amide,and carboxylic acid groups (B) paired with alkyl chains (A/n) makeexcellent ultraviolet photochromic candidates.

[0035] Short chain lipid-like compounds, where n=3, A is a methyl group,m=3 and B=COOH (see formula (3), above) form photochromic compounds thatturn red at room temperature when exposed to ultraviolet (254 nm) lightbetween 0° C. and 30° C. Long chain lipid-like compounds, where incombination n is between 4 and 20, A is a methyl group, m is between 2and 20 and B=COOH form photochromic compounds that turn blue whenexposed to ultraviolet light (254 nm) from as low as 0° C. to as high as100° C.

[0036] Symmetric compounds where the diacetylenic group is in a fattyacid form and is dimerized by bridging each fatty acid group through anamide linkage with ethylene diamine or 1,4-diaminobutane make excellentcandidates for photochromic agents due to their facile crystallizationand polymerization characteristics.

[0037] Mechanochromic agent enabling features: Mechanochromic agents canbe similar in structure to photochromic agents. A good crystallinematrix of the monomeric diacetylenic moiety is first formed followed byultraviolet polymerization (254 nm). For mechanochromic triggering, itis desirable to start with a highly ordered blue polydiacetylenicpolymer. Mechanical perturbation subsequently changes the blue form ofthe polymer to the red form. Other chromic changes such as conversion ofthe blue or red polymer form to a yellow form are also possible toachieve through intense and continued perturbation. Since only amechanical stress such as rubbing, sheering, compressing, or similarphysical means is required to cause a chromic change in the chromicagent and not a specific chemical reaction, the mechanochromic molecularstructure has few limitations.

[0038] The structure can be a simple alkyl chain, a fatty acid, anester, an amide, a carbonate group, a thiol, an ether group, apolyethylene group, a sugar, a carbohydrate, an amino acid or a varietyof other groups that do not adversely affect a mechanically inducedtriggering event. The ease of inducing a mechanochromic change isdictated by the selected structure. Rigid crystal structures with a highdegree of structural integrity of the mechanochromic polymer require ahigher level of mechanical perturbation to induce a chromic change ascompared with loosely packed crystal structures with weakerintermolecular interactions. For example, 5,7-hexadecadiynoic acid (16carbons in length) requires little mechanical pressure to induce achromic change in the polymer whereas 10,12-pentacosadiynoic acid (25carbons in length) requires several times more mechanical pressure toinduce a chromic change. Typically, the shorter the hydrocarbon chains(n and m less than 5) embedding the diacetylenic polymer the lessmechanical stress required to change its color. Weakly interactive headgroups or side chains such as esters groups (B) can be used to reducethe mechanical stress required to induce a chromic change whereasstrongly hydrogen bonding head groups such as multiple amides increasethe amount of stress required to induce a change.

[0039] The degree of polymerization (Z) can play an important role indictating the mechanical forces required to induce a chromic change.Short repeating units, caused from mild polymerization (e.g. where Z is3-10 units), can result in less required force needed to induce achange. Longer repeating units, caused by extensive ultravioletpolymerization, (e.g. where Z is from 50 to over 1,000), can result inrequiring significantly greater forces to induce a chromic change.

[0040] Thermochromic agent enabling features: A primary featuredictating a thermally induced chromic change is the melting transitionof side chains appended to the polydiacetylenic structure. Similar tothe mechanochromic example, shorter, more weakly interactive side chainstypically require lower heat levels to induce a chromic change. Longer,more strongly interactive side chains typically require higher heatlevels. In the case of thermochromically induced changes, it isdesirable to utilize side chain substituents most affected bytemperature changes. Lipids, waxes and other hydrocarbons can be used.In combination with side chain substituents, more strongly or weaklyfunctional groups may be used to adjust the thermochromic transition.

[0041] Ester groups, for example, exhibit weak intermolecularinteractions and are useful in lowering the thermochromic transitiontemperature, whereas amides exhibit strong hydrogen bonding interactionsbetween adjacent repeating units and find use to raise the thermochromictransition temperature and facilitate a reversible thermochromicreaction. Sugar molecules exhibit a high degree of intermolecularhydrogen bonding and can be used to synthesize high temperaturethermochromically reversible ingestibles (B) whereas polyethylene oxidesubstituents can be used as substituents (B) to synthesize lowertemperature irreversible compounds. Permutations of the hydrocarbonchain lengths (n and m) appending the diacetylenic unit can be used tofine-tune the desired temperature change setting.

[0042] The degree of polymerization (Z) also plays an important role indictating the temperature at which the chromic change will occur. Shortrepeating units, caused from mild ultraviolet polymerization (e.g.,where Z is 3-10 units), can result in lower thermochromic transitiontemperatures. Longer repeating units, caused by extensive ultravioletpolymerization, (e.g. where Z is from 50 to over 1,000), can result in asignificantly higher thermochromic transition temperature.

[0043] The compounds used to react with the carboxyl groups may beselected in relation to the ingestible to be modified. Thus, the groupsmay be chosen to make the polyacetylenes more compatible with theingestible, using polar compounds to enhance compatibility with polaringestibles, non-polar compounds to make the polyacetylenes morecompatible with lipid compounds, solubilizing groups which provide forsolubility or dispersibility, and the like. Certain photochromicmaterials can undergo a second color transition upon high heat (greaterthan 200° F.) from a red color to a yellow color and then reverse colorsupon cooling back to room temperature. Among such materials are the dualchain glutamate diacetylene containing lipids. Mono-amide glutamatelipids and tri-amide glutamate lipids can be used alone or incombination to achieve similar effects at lower temperatures. Forexample, the molecule can be modified to have strong hydrogen bondingcharacteristics that cause strong intermolecular interactions betweenmonomers along a polymer chain and exert a strong orderingcharacteristic along the chain. Strong intramolecular or interpolymerchain hydrogen bonding helps to stiffen and order the polymer backbone.Heading or perturbing the backbone cause a stochastic conformationalchange along the polymer that results in a color change from a highlyordered blue structure to a red disordered structure. Cooling orreversing conditions allows the intermolecular or intra-polymer chainhydrogen bonding interactions to dominate and re-order the polymer chainto an ordered blue structure. Among such materials are single chainlipids containing one or more amides for promoting intermolecularhydrogen bonding. For example, acetylated ethylenediamide-10,12-triconsdiyneoic amide contains two internal amide linkagesalong a single chain compound. Alternatively, dual chain lipidscontaining a mono-, di- or triamide glutamate head group can be used. Inaddition carboxylic acid lipids where the diacetylenic back bone is inclose proximity with the head group (1-4 carbon atoms removed) have alarge influence over the polymer structure and can exhibit reversibility(e.g. 4,6-heptadecadiynoic acid) at moderate temperatures (68° F. to130° F.). Reversible thermochromic materials can be made using glutamicacid with two chains of 10,12-tricosadiynoic acid to form a dual chainglutamate lipid. Dual chain glutamate lipids exhibit a high degree ofthermochromic reversibility due the interlocking nature of themicrocrystalline structure and/or their hydrogen bondingcharacteristics. Generally there will be from 1 to 10, more usually fromabout 1 to 8 hydrogen forming groups in a repeating unit of the polymer,such as amide, hydroxy, keto, amino, etc.

[0044] A chemical/structural balance between carbon chain length,position of the diacetylenic group along the carbon chain, hydrogenbonding due to the amide linkage, and head group structure can beachieved in the chromic change agent to give it characteristics ofreversibility, food compatibility, processing ease, color changemechanism, stability, and other factors beneficial to use as aningestible.

[0045] Diacetylenic forms of the chromic agent can be made into a hightemperature reversible material by creating a dual amide symmetriccompound where two long chain fatty acids (10,12-pentacosadiynoic acid)are bridged by an amide linkage by 1,4-butane diamine. The resultingmaterial forms a plastic/wax-like polymerizable material which remainsdark blue until it is heated above 150° C. Halogenating the even longerchain fatty acids along their methylene units can further raise thetriggering transition temperature to greater than 300° C.

[0046] Depending on the type of application, it may be desirable to havean irreversible thermochromic or physiochromic event or a reversibleevent. Hot liquids containing a reversible thermochromic material, forexample, can be made to turn red at a high temperature and back to blueat some intermediate or room temperature. Upon reheating, the liquidwould turn red again.

[0047] Cereals containing a low temperature reversible chromic materialcan be red at room temperature and change to blue upon addition of coldmilk. An irreversible thermochromic material can be used to show apattern change in a solid pastry indicating that the pastry was indeedheated to a certain temperature to reveal a message or picture whichstays the same even after cooling. Single chain monomers such as10,12-tricosadiynoic acid can be polymerized to form an irreversiblethermochromic property.

[0048] For lower temperature applications such as visualizing a colorchange when a food is brought to room temperature or above, it isdesirable to have a thermochromic compound which responds immediately toan ambient room temperature. 10,12-tricosadiynoic acid or10,12-pentacosadiynoic acid can be converted to the methyl ester form tocreate materials which change color from a deep dark blue toirreversible bright red, at about 80° F. These can be useful forindicating that certain foods, which should be stored at less than roomtemperature, have been raised or heated to higher than room temperature.For example, in some cases such as certain medications, dairy productsor foods, it is desirable to store them at room temperature or below andkeep them from being raised even slightly above room temperature. Inthese cases, it may be desirable to incorporate a thermochromicmaterial, which tells consumers that the product has at one time beenheld at an undesirably high temperature and should no longer beconsumed. It may be advantageous to have the thermochromic material indirect contact with the consumable medication or food and not withpackaging, so that no false indications are made, and precludingexpensive items from being disposed of inappropriately. Shorterhydrocarbon chains attached to the diacetylenic backbone can also beincorporated to reduce the energy or impact required to trigger achromic transition. A balance between the hydrogen bonding, Van derWaals interactions, charge-charge interactions, hydrophobic-hydrophilicinteractions, can be achieved to produce the desired type and situationfor color changing ingestibles.

[0049] Hydrogen bonding functional groups attached to monomers can beused to influence the chromic properties of corresponding polymers.Tightly hydrogen-bonding groups can increase the energy required for thechromic material to change color. Reducing the hydrogen bondingcapabilities of the chromic material can be used to reduce the energy ordegree of change in environment to cause a color change.Hydrogen-bonding groups include polar atoms, such as oxygen andnitrogen, to which the hydrogen is bound. Hydrogen bonding can bestructured between individual chromic molecules or between chromicmolecules and surrounding carrier materials with which they are inassociation.

[0050] Of particular interest are thermochromically revisable monomerssuch as N-ethanol-hexadeca-5,7-diyneamide andN-propylamineeicosa-5,7-diyneamide. These compounds when polymerizedwith ultraviolet light (254 nm), become deeply magenta colored at roomtemperature. When the polymers are raised above room temperature theybecome red/orange and when they are chilled below room temperature, theybecome a deep purple/blue color. The thermochromic transition ofN-ethanol-hexadeca-5,7-diyneamide is approximately 5° C. lower thanN-propylamine-eicosa-5,7-diyneamide. The lower temperature triggeringtransition was achieved by using an ethanolamine head group rather thana propylamine head group and using a shorter 16 carbon chain rather thana longer 20 carbon chain. N-ethanol-hexadeca-5,7-diyneamide findsapplication to color changing cereals where at room temperature thecereal will appear magenta/red and turn blue when cold milk is added tothe cereal. N-propylamine-eicosa-5,7-diyneamide finds application tocoatings on cookies where at room temperature the cookie appears a darkmagenta. When the cookie is touched, raising its temperature above roomtemperature, the cookie appears red. When the cookie is dipped in coldmilk, the cookie appears dark blue/purple.

[0051] High-temperature reversible chromic agents find multiple usesboth indicators that foods have been raised above a safe cooking level(e.g., one color will appear above 160° F.) and then subsequently asindicators that foods have been cooled to a level that makes them safeto eat without burning tissue in the mouth (e.g., the original colorwill reappear near 110° F.).

[0052] Chemical changes such as these provide for wide range of latitudeto modify the chromic agent for a particular triggering range andproduct application. Food or other ingestible products often havediscrete requirements such as shipping, storage, level of contaminants,acceptable moisture content or the like.

[0053] Irreversible color changes in polydiacetylenes can be introducedby eliminating or reducing the intermolecular or intra-polymer chainhydrogen bonding characteristics. For example, the polydiacetylenicmolecule can be a pure hydrocarbon structure without substituents, anester or have other relatively non-interactive groups. Additionally, thetriggering temperature can be dramatically reduced and made irreversibleby using short carbon chains such as 5,7-dodecadiynoic acid amidatedwith 2-(2-aminoethoxy)ethanol. The material is an oil at roomtemperature and will only polymerize at −10° C., where a blue polymercan be formed by ultraviolet irradiation (254 nm). Raising thetemperature above −10° C. causes the material to irreversibly turnred/orange. Materials such as these can find use in low temperature foodapplications.

[0054] Irreversible color changes are important to ingestiblescontaining them when it is desired to observe a color change at acertain temperature level and it is desired to maintain “memory” of thetemperature level achieved at a given time or location. It is convenientto use irreversible thermochromic color change in polydiacetylenesduring a temperature increase, converting the blue form of the color toa red form. For example, a thermochromic message can be revealed on atoaster pastry and the message is permanent until the pastry isingested.

[0055] Extended triggering conditions can be achieved inpolydiacetylenic compounds by creating unique structures includingattachment of constituent moieties such as sugars, amine acids orpeptides, DNA or RNA, polyether groups, binding pairs, or organic groupswhich can dominate the material's characteristics. Maximum temperaturetriggering ranges attainable can be extended to −30° C. or below togreater than 350° C., usually not exceeding 300° C. and not below 25°C., and more usually from between −20° C. to 250° C. For the purpose ofthis invention the range of interest will be from −15° C. to 225° C.,and particularly from −10° C. to 200° C.

[0056] Likewise, the substituents can be added to provide for othermeans to disrupt or order the polymer structure and thereby cause areversible or irreversible color change in the polymer backbone, asdescribed below.

[0057] Hydrochromic/solvatochromic agent enabling features: An importantfeature dictating the hydrochromic/solvatochromic nature of the chromicagent is the ease of degree to which the material can be effectivelyhydrated of solvated by a surrounding medium. The mechanism for inducinga hydration or solvation change can be accomplished either by affectingindividual substituent side chains or by hydrating/solvating completelayers adjacent to each other in the crystalline lattice. As with otherchromic change mechanisms, the ease or difficulty of inducing a chromicchange can be dictated by the integrity of crystal packing and thestrength of intermolecular side chain interactions.

[0058] Good hydrating side chain groups A and B include alcohols,polyethers such as polyethylene glycol terminated with an OH group,surfactant groups or the like. Solvation-induced chromic changes, wherepolar aprotic solvents such as acetone are used as the triggering agent,are effective when the side chain substituents are easily solvated withacetone. For example, n and m can be low in number (e.g. 1 to 3 units)and the head group can be a like kind substituent such as a ketone orester. Water-induced chromic changes are facilitated when both theintermolecular interactions between side chains and the intercrystallineinteractions between layers of the crystal lattice are affected bywater. It can be desirable to use symmetric compounds where A=B and n=mand both A and B are groups that are easily hydrated as well as groupswhich permit intercalation of water between layers in a crystal.

[0059] Mono- or multiple alcoholic groups can be introduced to promoteinteraction with hydrating or solvating solutions. Solvent orhydrochromic color changes are particularly attractive when combiningdry ingestibles with wet or moist ingestibles. For example, adding milkto cold cereal, dipping cookies or crackers in milk, adding crackers tosoup, pouring liquid syrups on breads or pancakes, adding saladdressings to salads, or the like, can be the trigger for a color change.

[0060] In addition, hydrochromic/solvatochromic effects can be used inunique ways to propagate a color change along a surface. As hydrationoccurs along an absorbent layer and the moisture migrates, a blue formof the polymer sensitive to solvation or hydration will turn thedisordered red of the polymer to the ordered blue form. Messages orgraphics can be visualized sequentially to create time-resolvedgraphical changes.

[0061] Ethylene glycol or polyethylene glycol groups can be attached tothe monomeric material to alter the solubility with different food typesor help emulsify the monomeric chromic agent. Ethylene glycol linkerscan range from a single ethylene oxide unit to 50 units. More typically,ethylene glycol linkers range from 2 to 20 units and most convenientlyfrom 3 to 6 units. The number of units can be changed depending on thedesired level of hydrophobic or hydrophilic nature for the resultingmolecule.

[0062] Standard hydrochromic/solvatochromic indicating groups can beattached in positions A and/or B to endow the base chromic change agentwith moisture-indicating properties.

[0063] pH sensitive and ionochromic change agent enabling features: Itis desirable to attach pH or ion sensitive substituent groups to thebase molecular structure such that a change in solution pH or ionicstrength in the surrounding medium can induce a chromic change in thepolydiacetylenic backbone. As with other chromic change mechanisms, theease or difficulty of inducing a chromic change can be dictated by theintegrity of crystal packing and the strength of intermolecular sidechain interactions. For example, groups that respond to ionic strengthsuch as a carboxylic acid can be used at positions A and/or B. It isdesirable to use shorter side chain lengths (e.g., n and m less than 4)in order to facilitate a higher degree of molecular mobility. Adicarboxylic acid where A and B are both COOH and n and m are both 1 to3 are of interest as ionochromic constituents since both ends of themolecule are affected during a triggering phase.

[0064] Groups susceptible to protonation or deprotonation or acid-basereactions are of particular interest. For example, A and/or B can be aprimary amine, secondary amine or the like. Changing the surroundingmedium from a neutral pH to an acidic pH can be used to cause a chromicchange in the medium. When A and/or B is an organic acid such as a monoor dicarboxylic form, treating the medium with a basic solution mayinduce a chromic change in the agent.

[0065] pH sensitive groups, e.g. bases and acids such as a hydrazide ora free amine group, can be attached to the head group of a lipid orhydrocarbon moiety to invoke a pH-triggering response from the blue formof the polydiacetylenic polymer to a red form of the polydiacetylenicpolymer. Ethylene glycol or polyethylene glycol groups can be attachedto the monomeric material to alter the solubility with different foodtypes or help emulsify the monomeric chromic agent.

[0066] Ethylene glycol linkers can range from a single ethylene oxideunit to 50 units. More typically, ethylene glycol linkers range from 2to 20 units and most conveniently from 3 to 6 units. The number of unitscan be changed depending on the desired level of hydrophobic orhydrophilic nature for the resulting molecule.

[0067] Standard pH-indicating groups can be attached in positions Aand/or B. Indicators specific to a particular pH unit are of interestsince they may find use as ingestibles to monitor saliva pH.lonophore-sensitive groups can be attached in position A and/or B toendow the base chromic change agent with ion-selective properties.

[0068] Chemochromic and biochromic agent enabling features: It isdesirable to attach chemically or biochemically sensitive and/orselective groups to A and/or B to give the chromic agent specificity tocertain chemical constituents in an ingestible matrix. As with otherchromic change mechanisms, the ease or difficulty of inducing a chromicchange can be dictated by the integrity of crystal packing and thestrength of intermolecular side chain interactions.

[0069] Examples of chemically selective groups can include cagedcompounds, chelating compounds, crown ether groups, peptides, DNA or RNAfragments, transition state analogs, binding pair members, or the like.Groups A and/or B can be more or less selective depending on theingestible application. The chromic agent can be made more or lesssensitive to chemical or biochemical triggering by increasing ordecreasing n and m, respectively; shorter chain lengths typicallyrequire of lower concentrations of the chemical or biochemical to inducea chromic change, whereas longer chain lengths generally require higherconcentrations of the chemical or biochemical required to induce achromic change.

[0070] Formulations and compositions: Monomeric or polymeric chromicchange materials can be combined with a carrier material to form acomposition which makes it possible for it to be applied to and/oradhered to foods. Carrier materials can range from a simple aqueoussolution to complex mixtures containing different emulsifiers, flavors,or foodstuff. Constituents such as oils, lipids, waxes, sugars, salts,lectins, agglutinins, protein matrices, carbohydrate matrices or thelike can be combined alone or together with an unpolymerized agent orpolymerized agent to give the agent the properties necessary fortransfer to, adherence with, or stability on a food type.

[0071] Carrier materials suitable for printing can include aqueoussolutions or pastes, which are applied and dried more slowly.Alternatively, the solution can contain an ethanol base, which can bedried more quickly. The carrier for printing can contain any foodcompatible composition.

[0072] Carrier materials suitable for extrusion can contain thickeningsubstances to give it the consistency for rapid extrusion and patternformation on the food surface of interest. Starches, methylcellulose,but pastes, dextrins, polydextrins, protein pastes, sugars, driedgelatins, rice papers, doughs, frostings, sugar-based papers, edibleinks, edible waxes, ingestible polymer substrates, caramelized sugars,or the like can be used for a support surface to which the chromic agentcan be applied. Thickened carriers provide for the ability to form threedimensional structures such as overlaying lines or patterns, that canenhance the contrast for the thermochromic or physiochromic colortransition. Carriers suitable for lamination can include substances thatprovide for stable layers to be applied to the food of interest.

[0073] Binding agents can be used to integrate more or less of thechromic material with a particular food type. In most cases, it isdesirable to bind the chromic material tightly to the food so that thematerial stays visibly in contact with the particular part of the foodportion it is initially on and that the material does not slough offinto a surrounding liquid or rub off on any packaging materials. Bindingagents can include sugars, carbohydrates, proteins, methyl cellulose,and other materials commonly used to bind food colors, coatings,frostings, sprinkles and the like. The binding agent can be co-mixedwith the chromic material, coated after application of the chromicmaterial to form a protective layer ,or used in combination with boththe food and the chromic material.

[0074] Various traditional, inactive ingredients can be used to co-mix,pre-color or adhere the chromic agent to a support surface on theconsumable product including: hydroxypropyl cellulose, hydroxypropylmethyl cellulose, microcrystalline cellulose, starch, red iron oxide,magnesium stearate, titanium dioxide, talc, colloidal silicon dioxide,polyethylene glycol, various synthetic polymers, Yellow 10 dye, carnaubawax, corn starch, sodium starch glucolate, or the like. These variousadditives are conventional and will be present, when employed, in arange of from about 0.1 to 95 weight %.

[0075] Configurations of application for chewable foods: The chromicmaterial, such as diacetylenes, need to be in a microcrystalline phasein order to polymerize to the chromic material. Therefore, if thediacetylenes are to be mixed with other components that adversely affectthe formation of the microcrystalline phase, the diacetylenes willnormally be prepolymerized before formulation. Solution phase chromicmaterial or monomer can be applied to a chewable food surface, dried andthen polymerized. Liquid phase monomer can be polymerized if in acolloidal/crystalline form, applied to a solid food surface, and dried.Solid microcrystalline monomer can be admixed with food carriers,applied to a solid food surface, and then polymerized. Solidmicrocrystalline monomer can be first admixed with a food carrier,polymerized, and then applied to a food surface. Solid microcrystallinemonomer can be first polymerized, admixed with a food carrier, and thenapplied to a food surface.

[0076] The solid surface of the food may be processed to accept themonomer or chromic material. In many cases, if the food surface is tooporous the monomer or chromic material will dissipate into theinterstitial spaces below the surface, rendering it unavailable forvisualization. Solid food surfaces can be prepared for accepting themonomer or chromic material by modification of the food composition orcoating the surface with a composition, which seals the food surface. Ineither case, application of the monomer or chromic material to the foodsurface will provide for a means to keep the material on the surface andvisible. Illustrative of such situations are sugars, proteins,digestible celluloses, methylcellulose, polydextrins, digestible waxesand gums, which can also be used to create a smooth hydrophobic barrierfor even coating of the physiochromic agent.

[0077] Structures containing the physiochromic agent can be createdwhich come in contact with the food type of interest. The structuresthemselves can be compatible with food and can be made with digestiblecomponents or can be made of material that is certified for contact withfood but not meant for consumption. Structures can be labels, part ofthe package, an insert in the package, paper rings, tabs or the like.The structures can be printed with the physiochromic material in a wayin which the structure can interact with the food. For example, thestructure can be an adherent label containing a thermochromic form ofthe agent. The adherent label can be adhered to a food type meant forheating. When the food is heated, the thermochromic agent will changecolor. If the label structure is edible, it can remain in contact withthe food type and be consumed along with the food. If the structure issafe for food contact but not edible, it can be part of a packagingmaterial or removed prior to consumption.

[0078] The monomeric or polymeric form of the chromic agent can be fusedor admixed into foods or medications. For example, a polymerizedliposomal or colloidal form of polydiacetylenic material can beprocessed with gelatin to produce a thermochromic form of desertgelatin. At refrigerator temperatures (40° F.), the gelatin could appeardark blue. When raised to room temperature (68° F.), the gelatin wouldturn bright red/orange. Alternatively, a polymeric chromic agent couldbe cast into a throat lozenge. A chromic agent that undergoes atemperature transition from dark blue to red/orange at 100° F. could beemployed to help a consumer determine if they have a fever. Usage of thelozenge would indicate to the consumer that they have a low grade feverif the lozenge turns red/orange. The consumer could also examine histongue to see if either a red or a blue color has come off the lozenge.Blue would indicate no fever and red/orange would indicate a low-gradefever. Similarly, chromic change agents can be incorporated in tablets,pills or other medications formulated to be taken by a sick patient, andcan indicate the presence of a fever by a color change, which remainswith or comes off the medication.

[0079] The thermochromic material can be patterned alone or incombination with food-based inks to create bar codes. Bar codes can beutilized in connection with cooking where the cooking system, equippedwith a bar code scanner, can measure a change in the bar code as thecode is exposed to high temperatures. Bars on the code can be made tochange color when one or more temperatures are achieved. The opticaldensity change in a given bar will result in a prescribed change andinterpreted by the measuring system to indicate a specific temperature.The bar code can indicate doneness or in process cooking. The bar codecan be printed directly on the solid food type or on the food packaging.This allows the bar code and bar code reader to be used as a temperaturemeasure device.

[0080] Methods for triggering color change: The chromic change can betailored to match a desired effect or outcome in a particular food oringestible. Color change triggering processes can include temperature,pH changes, changes in ionic strength, mechanical changes such as stressor pressure during mixing or contortion, chemical changes such as theaddition of a second component, exposure to light for a photochromiceffect, biochemical reactions such as binding pair interaction, solventenvironment changes, hydration or dehydration, solvent changes, andenzymatic changes where enzymes in the food can induce a change. Themethyl or ethyl ester of 10,12-tricosadiynoic acid or10,12-pentacosadiynoic acid is made by standard esterification inmethanol or ethanol respectively. The ester compound can be applied tofoodstuffs, crystallized and then polymerized at or below roomtemperature.

[0081] Physiologic changes in pH, ionic strength, or hydrogen bondingagents can be used to alter the state of the chromic material, which maybe induced by finger touch or contact with saliva. Saliva is relativelyacidic and can be used to induce an acidic environment which can cause achromic change in foods containing the chromic material. The darkchromic material is extremely sensitive to thermal contact and changescolor immediately at 70° F. for the tricosadiynoate ester and at 80° F.or above for the pentacosadiynoate ester. The chromic material can besensitized to respond to physiologic temperatures (i.e., about 98° F.for humans).

[0082] Physiochromic matrices can be formulated to hold the chromicagent in one state until the matrix is dissolved. Once the matrix isdissolved and its effect on holding the chromic agent in one state, thechromic agent is free to change conformation to another state. Forexample, an acid sensitive, pH reversible physiochromic agent can bedried down with an acid. The acidity can hold the polymer in one coloredstate. The local concentration of acid is high in the dry state. When aphysiologic buffered solution is added, the acid is released andneutralized by the buffer. The physiochromic agent can now covert to analternative color since it is bathed in a basic environment.

[0083] Combination colors can be integrated along with the chromicmaterial to create a variety of color change effects. For example, thebrown color used in a variety of food types is made with a combinationof yellow, red and blue. The blue food color can be replaced with a blueform of the chromic agent. Upon color change triggering, the brown foodcolor combination can be converted to a bright red-orange. Examples ofbrown colored foods or beverages include brownie mixes, hot and coldchocolate drinks, cinnamon colors, and the like.

[0084] The physical, conformational, or polymerization state change canbe used as a mechanism to release or change certain embedded flavors,nutrients, aromatic compounds, nutraceutical agents or the like. Forexample, a flavor material can be chemically coupled to a monomernon-chromic form compound. In the monomeric form the compound-flavoringexpresses a flavor, whereas upon polymerization the monomer becomespolymerized, consequently restricting the flavoring to interact withtaste receptors. The restricted form of the flavoring becomesnon-flavored. The release mechanism is simultaneously traced with aphysiochromic color change as an indicator.

[0085] Alternatively, conformational changes in the chromic materialmatrix can be utilized to release various food grade compounds. Forexample, polydiacetylene in its blue form is highly ordered on themolecular level. During processing and polymerization, a food gradecompound such as a vitamin or flavor can be trapped. Upon temperature orphysiochromic triggering of the polydiacetylenic material to the redform, the polydiacetylene becomes disordered and opens at variouspositions. During the conformational disordering of the polymer, thevitamin or flavor can be released. The monomeric form of the chromicmaterial can be used to absorb and allow in the flavor or aroma.Polymerization could be used to trap in the flavor or aroma. The orderedblue form of the polymer may hold a flavor or aroma where heatingresults in a conformational change and disorder in the polymer which isuseful to release the flavor or aroma.

[0086] Specific physiochromic changes may be desirable when developingfoods that a producer would like to differentiate from a competitors.Binding moieties can be used to facilitate specific photochromic,thermochromic, or physiochromic color transitions. Lectin-receptoragglutinin-receptor, antibody-antigen, biotin-avidin interactions or thelike can be used to stimulate a binding pair interaction betweendifferent food components. Binding pair interactions can be used tocreate specific colorimeter changes in the chromic agent. For example, acombination of milk and cereal can be formulated in which a specifictype of milk contains one member of a binding pair, such as a multiplebiotinylated milk protein and the cereal contains a biologically activeform of the physiochromic agent that contains avidin or streptavidin asa second member of the binding pair. When the specific milk comes incontact with the specific cereal, then only that milk will cause thespecific cereal to change color through the binding interactions of thebinding pair members. No other milk or cereal combinations could cause achromic change without the selective interactions of those binding pairmembers. This scenario can help food manufacturers create novel means ofbrand differentiation.

[0087] Carbonation pressure release in opening sealed carbonatedbeverages may be used to induce a local stress/concentration change,which could cause a color triggering changes in the chromic material.For example, the inside of a liquid container can be coated with a pH orfriction sensitive version of the physiochromic material. Upon openingthe container and release of built up pressure to ambient conditions,the process of bubble nucleation and local carbonic acid concentrationchange may be used to cause a change from environmentalcondition/conformation of the color change agent to another form of thematerial. If the container is clear, the color change can be madeevident to the observer of the color change. The color change agent caneither be in a water solution form such as contained within a liposomestructure or be coated on the inner wall of the container.

[0088] For hydration-activated color change, physiochromic agents whichchange color depending on the degree of solvation or hydration can beused (hydrochromic agents). Color change agents capable of changingcolor upon partial or complete hydration and can be ingestible can findmultiple uses for food or food related products. For example, thebi-polar diacetylenic compound 4,6-decadiyne-1,10-diol when adhered to asurface and polymerized at room temperature forms a deep blue/purplepolymer. The blue/purple polymeric form of the material changes to ared/orange color upon hydration below or above the melting transition ofthe material. One mechanism for inducing the color change may be rapidintercalation of water between the layers of the crystalline latticewhere the aqueous phase disrupts the ordered polymer lattice.

[0089] The hydrochromic agent's rate of color change is temperature andconfiguration dependent. For example, the rate of color change from theblue/purple color to a red/orange color is rapid and occurs within aminute when a thin layer of the hydrochromic agent is uniformly spreadover a dry porous structure and exposed to an aqueous fluid at or 10° F.below the melting transition of the material. The color change is slowedsignificantly from one to several hours if the hydrochromic agent isapplied in a thick layer (0.1 to 1.0 mm) and treated with an aqueoussolution near freezing.

[0090] The hydrochromic agent can be placed on -an ancillary materialsuch as carbohydrates, granulated sugar, sugar sprinkles, fondant, sugarpastes, candies, nutritional bits, food coatings, condiments, carriers,emulsifiers, coating materials or the like and subsequently applied to afood surface. For example, the diacetylenic compound4,6-decadiyne-1,10-diol can be conveniently dissolved in an alcoholicsolution (0.15 g/ml) and the solution applied to white or colored sugarsprinkles. Upon coating, drying and polymerization, the sugar sprinklescan subsequently be adhered to a cookie, cereal, candy, bread, cake orthe like. The dark blue/purple sprinkle changes to an orange/red colorimmediately upon treatment with water, milk or other liquids capable ofdisrupting the crystal packing of the chromic agent.

[0091] The use of hydrochromic agent pre-coated sugars, salts or othercarriers has the advantage of providing a high degree of coloration andsurface area for fluid contact. For example, a fine hydrochromic/sugarparticle coating creates capillary channels for fluid to wick through,thereby facilitating the hydration process.

[0092] Other structures may also conveniently contain the hydrochromicagent placing it in close or intimate contact with foods. For example,the material can be placed on a bowl, spoon, plate, fork, straws, ahydrating strip, a package insert, part of the package or the like, suchthat a portion of an absorbent material can be in liquid contact with aningestible liquid. As the liquid hydrates the structure, the liquidsolvent hydrates and migrates along the structure causing thephysiochromic agent to change color. If the structure containing theagent is edible, it can remain in contact with the ingestible liquid andbe consumed. If the structure containing the agent is safe for contactwith food, but inedible, the structure can be removed prior toconsumption of the ingestible liquid.

[0093] Mechanical/frictional means can be used to induce color changesin a variety of food compatible products. Color changes can be inducedusing mechanical means primarily including friction due to rubbing,elasticity, and shearing. For visible friction-induced color changes,the color change agent can be permeated into or placed on a surface.Rubbing, stretching, and shearing or other stress-causing action alsocan be used to induce a frictional force on the color change agentresulting in localized heating. The ease and magnitude of color changeis dependent on the transition temperature of the chromic agent, thefriction coefficient between the molecules in the composite or a rubbingtool and the thermal insulative/conductive properties of the compositeor rubbing tool. Rubbing tools can include a person's fingers, fingernails, teeth, a wooden stick, a plastic implement or the like. Materialsthat are more thermally insulative may result in more thermal energyremaining with the chromic agent and less being transferred to thecomposite or rubbing tool. Metal rubbing tools serve as poor devices forinducing a frictional color change, whereas insulative materials such asplastic or wood provide an easier means for inducing a color change.

[0094] Mechanical/frictional color change methods are attractive forrevealing messages, altering graphics, introducing codes, creatingsweepstakes, creating entertaining graphics or the like.

[0095] Touching, rubbing mixing, chewing, kneading and various otherforms of handling can be used to induce the color change. The colorchange agent must be responsive to the available amount of frictionalforces. The agent must also be stable to ambient temperatures andhumidity conditions or a color change may result from influences otherthan frictional/mechanical forces. An exemplary compound, the bluepolymeric form of 10,12-octadecadiynoic acid exhibits good thermalstability up to 100° F. with full hydration, whereas rubbing the dryform of the blue polymer easily triggers the polymer to the red form ofthe polymer.

[0096] Mechanical/frictional triggering can be performed directly on afood surface, on a laminate in contact with the food or on a genericsurface. In each case, the triggering process can be used to revealhidden messages, illuminate branding messages, provide a means ofinteractive graphical changes or the like.

[0097] The mechanochromic material can be applied to a surface by avariety of means including application of a solvent containing thechromic agent by means of ink jet printing, spraying offset printingprocesses, blotting, pad printing, dipping or soaking. Concentrations ofthe chromic agent can be from about 2 g/ml to 0.01 g/ml, typically inthe range of from about 1 g/ml to 0.05 g/ml, usually from about 0.5 g/mlto 0.1 g/ml. Alternatively, the chromic agent can be applied usingtransfer methods such as thermal transfer, rubbing from a solid, from amolten liquid or the like.

[0098] Photoactivation can be used to cause color changes in foods orfood-related products when an appropriate photochromic agent isintroduced. Convenience foods containing a photochromic agent whenplaced in sunlight provide an entertaining means to create a variety ofeffects. For example, cookies, cereals and various other conveniencefoods can be used to reveal, various logos, branding identities, codes,sweepstakes information, messages or co-merchandising items to theconsumer.

[0099] The photochromic agent can be patterned on or applied to thefood, packaging material or implement in contact with the food by meansdisclosed earlier. Photochromic agents have the advantage of notrequiring incidental heat of fluids to create a visual effect. Dependingon the photochromic agent, the food can either turn from a natural foodcolor to a new hue or from a given hue to an alternate hue.

[0100] For thermochromic agents, temperature ranges can include coldtemperature for frozen and then thawing (−20° F. to above 32° F.), lowtemperatures from refrigerator levels to room temperature (33° F. to 60°F.), moderate room temperatures to moderately above room temperature andoverlapping temperatures from (61° F. to 100° F.), and room temperatureto moderate to high cooking temperatures (70° F. up to 200° F.). Thefinal temperature triggering range for the chromic agent is dictated bythe hydrocarbon chain length of the molecule, the intermolecularhydrogen bonding capabilities of the molecule's bead group, additionalside chains of moieties which influence intermolecular attractions orrepulsions or the like, environmental effectors which impact the finaltemperature triggering transition for the chromic agent, and the degreeof polymerization to which the chromic material is exposed. Guidelinescan be given, but for a particular transition temperature change, theactual change must be determined experimentally. One can try differentamounts of the effectors and graph the effect of the concentration ofeffectors with the change in transition temperature. A curve is producedwhich allows the determination of the amount of effector, with thechange in transition temperature.

[0101] Environmental effectors combined with chromic agent to increaseor decrease the thermochromic transition of a given thermochromic agentinclude: various oils, waxes, low levels of organic solvents such asalcohols, ketones, ethers, chloro- and fluorocarbons, metal ions andother ionic compounds, chelating compounds, emulsifiers, or the like.The effector material can change thermochromic transition by alteringthe energy required to induce a thermochromic transition in the agent.Oils and organic solvents can interact with the long chain hydrocarbonsof a C23 or C25 polydiacetylenic acid. The chain packing can bedisrupted by the effector to create a metastable state in the polymerthat can, in turn, change color at a lower temperature. For example, thetemperature transition can be lowered for a polymerized C25polydiacetylene polymer in its native dry crystalline state from atemperature range of 150° F.-170° F. (depending on the degree ofpolymerization) down to 120° F.-130° F. by suspending the crystals in asugar syrup and adding trace amounts of ethanol. Concentrations of oilsor solvents added to a matrix can be from 0.001% to 100%, based on 100%of diyine, more usually from 0.01% to 50%, and typically from 1% to 10%.

[0102] The melting transition of the wax or oil in contact with thechromic agent can directly increase or decrease the intrinsic transitiontemperature of the chromic agent. Oils that solidify under freezingtemperatures can stabilize the chromic agent. Upon a temperatureincrease above melting transition temperature of the oil or wax, themelting process can facilitate the melting of a hydrocarbon side chainon the chromic agent, causing it to undergo a thermochromic transition.The final thermochromic agent triggering temperature can be furtheradjusted by selecting a specific temperature at which polymerization ofthe chromic agent is performed. Polymerization at subzero temperatures(−10° F.) lowers the final triggering temperature relative topolymerization at temperatures just above freezing (10° F.).Thermochromic transition temperatures can be increased by increasingintermolecular stability, such as promoting hydrogen bonding ofhydrophobic interactions, both between monomeric units within a giventhermochromic polymer chain and between the polymer chain and a giveneffector molecule. For example, the transition triggering temperature ofa C23 or C25 polydiacetylenic acid polymer can be increased by embeddingthe polymer in a high temperature-melting paraffin or wax. Thethermochromic material can be embedded in waxes from a concentration of0.01% to 99%. More usually from 0.1% to 50% and typically from 1% to10%.

[0103] Alternative chromic agent triggering mechanisms and colorreporting processes: Alternative triggering mechanisms include the useof enzymes or pre-digestive effectors primarily from saliva which canchemically or biochemically induce a color change in the chromic agentthrough a catalytic change. For example, enzymes responsible for theinitial stages of starch break down occur in saliva. Chromic agentschemically modified with starch or carbohydrate chemistries can be madesusceptible to enzymatic activity resulting in a conformational orenvironmental change which in turn can cause a color change in thechromic agent.

[0104] Microbial metabolites, enzymes, or by-products find use as atriggering mechanism for the chromic agent resulting in a means todetect certain bacteria in foods. For example, the chromic agent can bechemically modified to respond to certain by-products produced bySalmonella. The chromic agent is placed near or coated on the innersurface of a wrap that is in contact with a processed chicken carcass.If Salmonella is present in the carcass and produces a triggeringcompound the chromic agent is triggered, indicating the presence ofSalmonella.

[0105] An alternative mechanism for microbial detection is the use of athe microbial cell's uptake of monomer forms of the chromic agent. Forexample, E. coli can use diacetylenic fatty acids as a carbon source.Incorporation of the polymerizable acid into a bacterial cell membranecan be detected by ultraviolet irradiation of the bacteria resulting inpolymerization of the acid to a blue color. Food processors can simplyirradiate food; development of blue color indicates the presence ofharmful bacteria.

[0106] Importantly, polydiacetylenic materials as a class of intrinsicchromic change agents can be selectively tuned to respond to specifictriggering processes relevant to ingestible products. Additionally,polydiacetylenic materials can uniquely undergo multiple differentsequential color changes. Examples include photochromic triggeringfollowed by irreversible thermochromic triggering; photochromictriggering followed by reversible thermochromic triggering; photochromictriggering followed by mechanochromic triggering; reversiblethermochromic triggering followed by irreversible chemochromictriggering; multiple thermochromic transitions during increasing ordecreasing temperature exposure; and other permutations.

[0107] Configurations for liquids: Liquid phase monomers can be includedin an unpolymerized form in a beverage or consumable fluid, such as in asyrup where the monomer is in a colloidal or microcrystalline state. Themonomer can be directly polymerized with an ultraviolet light source orsunlight. The solution suspension monomer can also be pre-polymerizedand then added to a liquid phase consumable. The monomer can be madewater-soluble using short chain compounds, which are mono- or bi-polar.In this case, the monomer must be prepolymerized in a solid form andthen solubilized after polymerization. Polydiacetylenes undergo atopochemical polymerization and must be in a crystalline state in orderfor polymerization to occur. Monomeric lipophilic forms of diacetyleniccompounds can form colloidal particles, such as liposomes, vesicles, orother lamellar forms. Lipophilic forms of the monomer can becrystallized in a colloidal state and polymerized while the monomer issuspended in an aqueous solution. Colloidial or microcrystallinesuspensions of monomeric diacetylene can be made using ultrasonicationor standard reverse phase vesicle formation methods. Heating and coolingcycles along with intense sonication can be useful for improvinguniformity and homogeneity of the suspensions.

[0108] For alcoholic beverages, the monomer can be processed into thebeverages using reverse phase vesicle formation. The monomer can bedissolved in ethanol and combined with the beverage aqueousconstituents. Vesicle formation can be accomplished using standardprocesses. After the beverage has been formulated, polymerization of themonomer can be accomplished using standard polymerization methods.

[0109] Methods for application to foods: Compositions containing eitherpre-polymerized material or monomer material can be processed into foodsusing a variety of application methods such as ink jet printing, padprinting, extrusion, spraying, liquid applicators, dip coating,sublimation, spreading, application of laminates containing the materialsuch as sugar layers or rice paper, edible labels, dripping, dyesublimation printing or the like. The method of interest will depend onthe food substrate utilized, the composition to be applied and thedesired format in which the composition is to be placed.

[0110] Coating Matrices and coating methods for sugars, salts, shreddedand powdered cheese, flower, grains, nonpareils, and other powderedforms of foods. Polyethylene glycol coating matrices for cereals andcookies are practical due to the unique solubility properties ofpolyethylene glycol polymers.

[0111] Co-coating matrices can have the combine properties of helping toadhere the chromic agent to a food type, suspending the chromic agent ina matrix to maximize the visual appearance of the chromic agent, helpingto modulate the activity and performance of the chromic agent, helpingto minimize the amount of chromic agent required, and the like. Forexample, the coating matrix can have the property of allowing thechromic agent to undergo a conformational transition from one color toanother by providing the necessary flexibility required by the chromicagent.

[0112] The coating matrix can also provide a source of inducing defectstructures in the solid phase of the chromic agent or as a means forintroducing doping agents along with the chromic agent as enhancers toimprove the agent's optical performance. Doping agents can be used toenhance the optical properties of irreversible and reversible chromicagent changes. Low levels of additives can be used to enhance thecolorimetric changes that the material can undergo. Doping materials caninclude chemically/structurally related compounds which help create amolecular environment favorable to the transitions necessary for thechromic agent to undergo changes during its transition from one color toanother.

[0113] The coating matrix can also help provide a protective barrier forthe chromic agent by minimizing the unwanted effects due to oxidation,moisture, or stabilization of the chromic agent of effectors of thechromic agent during storage and shipment of the final end product tothe consumer or during product production.

[0114] Coating matrix solutions can be made using a variety of solventsincluding polar protic solvents such as water ethanol and methanol,apolar organic solvents such as dichloromethane, polar aprotic solventssuch as acetone, or the like. It is desirable to use solvents that areconsidered food grade such as non-denatured ethanol.

[0115] For application to cereals, it is desirable to place thephotochromic, thermochromic, or physiochromic material in a carriermaterial such as a sugar matrix whereby the matrix is applied as acoating to the cereal during production. For application to conveniencefoods such as flat pastries or cookies where patterning is important,high-speed printing techniques are important. In this case it isdesirable to use a soluble form of the material so that it can beincorporated directly into the liquid matrix used for printing.

[0116] The monomer or polymeric material can be applied to a solid foodusing a laminate overlay where the base material in the overlay/laminateis itself edible and contains the monomeric or polymeric color changematerial. Rice paper can be used as a laminating material which whenwetted and containing the polymer can be easily adhered to the food as asubstrate. Laminates can contain the chromic agent in combination withsugars, carbohydrates, digestible polysugars, or proteins, which givethe laminate a stable layer. The layer can have the property of beingdirectly layered on to a food surface, fused and then activated forphotochromic, thermochromic or physiochromic activity. Food laminatescapable of containing the chromic material can be any commerciallyavailable product or formulation that is physiologically acceptable andcan be printed or coated. For example, the laminate can be a marzipansheet available through most bakery supply sources. The thin sheet canbe printed, stamped, blotted with the chromic material by any convenientmeans, dried and polymerized. The laminate can then be adhered to thefood type surface alone or with food pastes.

[0117] Commercially-available laminate/paper materials compatible withink jet printing can be used (Kopykake, Torrance, Calif.).Commercially-available ink jets can be modified to contain an inkversion of the chromic agent. The ink jet cartridge can be used with anaqueous or solvent-based solution containing the chromic agent. The foodgrade laminate/paper can be inserted into the ink jet printer andstandard ink graphics printing programs utilized to generate text andgraphics. The laminate approach provides a means for generatinghigh-resolution graphics and text and transferring the images or textdirectly to the food type. The laminate can be made to be compatiblewith the food flavor and texture. For example, it is desirable to have asugar-based laminate for sweet products such as pastries, cookies, andcertain convenience foods. Alternatively, it is desirable to have asalt/seasoning-flavored laminate for dairy or processed meat products.The exact composition, flavor, and texture of the laminate will dependon the food component into which the chromic material is integrated.Laminates have the advantage of being separately prepared from the foodproduct and then processed to be a part of the food. Parallel processingprovides for high-speed production and simplified implementation.

[0118] Edible food grade labels, paper or wrappers containing thechromic material can be used for a wide range of general applications.The label can be made with a digestible carbohydrate material ratherthan a non-digestible cellulosic material. Printing the chromic materialcan be accomplished by standard printing means. The printed chromiclabel can be applied to any solid and reasonably flat surface such as acookie, a toaster pastry, baked goods, and a variety of conveniencefoods. A major advantage to chromic labels is that they can be pre-massproduced and subsequently applied to finished foods rather thanrequiring changes in existing food production processes. The chromicmaterial can made soluble in ethanol or various highly volatilesolvents, which can be quickly evaporated, or in an aqueous solution,which can be absorbed. In any case, it is desirable to coat the surfaceof the food substrate with the chromic material so that uponpolymerization the chromic material is highly visible. The substrate canbe dipped into a solution containing the chromic agent, thereby coatingthe agent on the substrate's surface.

[0119] Entertainment foods such as marshmallows can incorporate thechromic material using dip coating or spraying processes to provide anextra level of enjoyment, especially for children. Chromic marshmallowscan be produced to respond to ambient temperatures such as touch orelevated temperature fluids, like hot chocolate. Marshmallows can bedirectly dip coated with a higher temperature thermochromic materialdissolved in an alcoholic solution. After drying and polymerization toproduce the dark colored chromic agent, the marshmallows would remaindark until exposure to high temperatures such as an open flame. Uponexposure to any elevated temperature, the dark marshmallow would turnbright orange-red.

[0120] Alternative means of incorporating the chromic agent into foodscould include biochemical substitution. Fruits, vegetables, certainmeats, bacterial cultured dairy products such as yogurt, grains, rice,beans or other amenable foods can be grown with the precursor monomericmaterial as a nutrient for the growing food. Upon incorporation orbiochemical uptake of the precursor monomer through the appropriatepathway into the food product, the food can be irradiated withultraviolet (254 nm) to cause polymerization of the foodstuff. Variousdairy products such as cheeses, milks, and yogurts that naturallycontain bacterial cultures to aid in digestion can be made withmonomeric and/or polymeric chromic agents.

[0121] Spectral colors relating to chromic change agents: The color,contrast, and hue can be adjusted to give a chromic change agentparticular visual characteristics. Color change characteristics can beachieved by changes in the chromic agent itself or in combination withstationary base colors associated with the same matrix as the chromicchange agent. Various permutations of base colors in combination withthe initial color of the chromic change agent will give one visual colorto start with and often an unexpected color with which to finish.Chromic change agents with chromically reversible properties can be usedto achieve repetitive visual effects compared to irreversible chromicchange agents that can be used to achieve a one time effect.

[0122] Standard Pantone Colors, RGB, CMYK and colors typically used inthe food industry can be used in combination with the chromic changeagent. Examples of color change options based on the change of thechromic agent alone (white or clear base color) or in combination with aother base colors listed below but are not limited to any specificexample are shown in Table 1.

[0123] In addition, color additives such metallic flakes, glitters,sparkles, and other elements which augment colors, can be used to createdesirable visual effects. For example, silver coated non-pareils can becoated with a red reversible form of the chromic change agent to givethe effect of a shiny red anodized sphere. When the combination iscooled, the coated non-peril appears to have a dark blue metallicanodized coating. TABLE 1 Color change options based on initial chromiccolor and base color. Initial Chromic Color Base Color StartingCombination Triggered Color light blue white/clear light blue pinkmedium blue white/clear medium blue orange dark blue white/clear darkblue red/orange magenta white/clear magenta red magenta white/clearmagenta blue red white/clear red blue red white/clear red yellow yellowwhite/clear yellow red blue yellow green orange pink yellow magentagreen red yellow orange brown orange orange dark orange dark brownorange light blue purple dark blue orange light green red/green graygreen orange pink red purple red tan deep red blue/purple light bluelight green gray green red/green yellow red orange red yellow light tangolden brown red light blue brown orange red light green brown navy blue

[0124] Food grade metallic and pastel colorants (Linton Paper & Supply,Inc.) can also be used in combination with the chromic change agent togive a sparkle-like effect. More granular colorants can be used to givea matte-like finish to the coating.

[0125] Methods for polymerization: Polymerization can be accomplishedeither prior to processing with the food or after the monomer has beenprocessed with the food. The photochromic properties of the chromicmaterial can be used to create patterns and messages on the surface ofsolid foods. Increasing or decreasing the level of polymerization of thechromic material is used to increase or decrease, respectively, thetemperature or other means of inducing color changes in the polymer:foodmatrix or the like used to trigger a chromic change in the material. Forexample, different zones of a food surface, which contains the chromicmaterial, can be polymerized to different levels. Each zone can,depending on the level of polymerization exposure, change colorsequentially as the temperature rises. The chromic change zones can tellconsumers that cooking is in progress but not yet done. As cookingcontinues and as the last zone changes color, the consumer can ascertainthat cooking is complete.

[0126] Zones which change colors at increasing temperature can be usedfor food safety purposes indicating to preparers or consumers when thefood is cooked to a temperature level and any contaminating bacteriahave been killed (e.g., 160° F.). Zones would be calibrated toaccommodate higher external temperatures during cooking.

[0127] Increasing or decreasing the localized concentration of chromicmaterial in combination with controlling the local level ofpolymerization can be used to create complex patterns on the surface ofa food type. Increasing the local concentration in one area relative toanother area will create a higher relative triggering temperature in thehigh concentration zone relative to the lower concentration zone. Thepatterns can be developed to create the visual appearance of a changinggraphic throughout the temperature triggering process.

[0128] In addition, standard food colors can be used in combination withthe chromic material to create full color designs and patterns. Thevisual representation of a graphic that changes color and apparentpattern throughout the heating process can have significant value inthat it can be used for commercial, promotional, merchandising andadvertisement purposes. In some cases, polymerization can beaccomplished by the consumer where, by opening a package and placing thefoodstuff in sunlight, a color begins to appear immediately prior toconsumption. For example, drinks or cookies can be made to change colorin the sun. In other product formats, the photochromic food may bepurchased along with an appliance or hand held ultraviolet lamp whichcan be use to expose the photochromic material.

[0129] Thermal polymerization can be utilized in certain foods. Thermalpolymerization provides for photochromic color development of thechromic agent without the need for an external ultraviolet light source.Certain forms of diacetylenic compounds that are highly ordered, yetprovide flexibility for reorganization, can self-initiate polymerizationunder mild conditions. For example, the crystalline form of themethylester of 10,12-tricosadiynoic acid will polymerize in the dark andin absence of ultraviolet light. The thermal polymerization temperaturemay be substantially different from the thermal color change transitiontemperature. Polymerization may occur at a lower temperature, e.g.10-20° F., than the thermal transition temperature.

[0130] Patterns in the chromic agent can be generated by selectivelyplacing the agent in locations using methods such as ink jet, pad,extrusion or offset printing followed by polymerization of the chromicagent. Alternatively, the patterns can be generated using a continuousevenly coated area of the chromic agent followed by photo-maskingtechniques. Ultraviolet light-transmitting photomasks can be utilized.In either case, high-resolution graphics and line art can be generateddirectly on the food surface.

[0131] Ingestible chromic change particles dispersed throughout groundmeats as an intrinsic internal thermometer: The United States Departmentof Agriculture now recommends not using the color of cooked ground meatsto determine doneness and whether or not that the meat has been cookedto a safe level (greater than 160° F.). The chromic change agent canfind use as an element dispersed throughout ground meat that turns coloronly when the center of the ground meat has reached an internaltemperature of 160° F. The chromic agent can be coated on any compatiblefood grade additive that can be admixed with the ground meat prior tocooking. The chromic change agent/additive can be introduced into theground meat at the meat processor level or by the consumer immediatelyprior to cooking. Chromic change agent particles can be dispersed intoground meats at a concentration that allows the particles to bevisualized any time the meat is exposed when cut open. The chromicchange agent particles can be dispersed at a concentration of one percentimeter cubed to a concentration of 1000 per centimeter cubed. Moreoften the chromic change agent particles can be dispersed at aconcentration of 10 per centimeter cubed to 500 per centimeter cubed.Usually, the chromic change agent particles should be present from aconcentration of 25 per centimeter cubed to a concentration of 100 percentimeter cubed. Chromic change agent particles obviate the need forthermometers since the meat itself can posses the temperature sensingcapability. The cook or consumer need only cut into a piece of meatduring cooking to determine accurately the internal level of doneness ofthe meat being cooked.

[0132] Ingestible chromic change particles integrated into foods mayfind broad use in cooking or warming other items as well. For example,they can be used for baked goods, in food service for monitoring holdingtemperatures, processed, precooked meats such as hot dogs, in foodprocessing, in microwaveable foods, and various other related productsor processing.

[0133] The chromic change agent can be conveniently coated onto aparticle such as a spice, sesame seed, oatmeal flake, protein particle,soy based particle, carbohydrate particle or any other food compatiblematrix particle that is of size which can be identified by eye. Thechromic change agent can be coated as a film on the surface of theparticle to give the particle a characteristic color that isdifferentiated from the ground meat with which it is admixed.

[0134] Chromic change agent particles can range in size and shape.Typically the chromic change agent can be a sphere, a disc, egg shaped,a flake, a random globule, a ring, various geometric shapes, a rod ornoodle shape, or the like. The chromic change agent particle can be assmall as a 0.5 millimeters along its longest axis so as to be visible byeye to as long as sever centimeters. More usually the chromic changeagent will one to 10 millimeters along its longest dimension andtypically 2-5 millimeters in length.

[0135] Chromic transition conformational change as a depot releasesubstance: The chromic transition may be used as a releasing mechanismfor nutrients, vitamins, ingestibles, drugs or the like base on thestructural change that it can undergo when it is triggered from onecolor to another. For example, polydiacetylenic material is known toundergo a significant conformational change during its transition fromone color to another. The blue form of the polymer is well orderedsystem comprised of parallel strands of extended and conjugated doubleand triple bond units. Side chains and substituents are ordered alongwith the polymer backbone in a lattice structure. When the orderedmacromolecular structure is chromically triggered, it becomes disorderedand an open lattice. The chromic change mechanism can be used as a meansto release a substance embedded within the lattice matrix. Opening thematrix can be used to release the embedded constituents. The chromicprocess has a dual function: first, it can act as a releasing mechanismand second, it serves as a color change indicator as to when the releaseoccurs.

[0136] Wording or graphics printed on the side of over-the-counter orprescription drugs can be printed with a low temperature irreversiblethermochromic material, indicating to the consumer, pharmacist ormedical specialist that the drug has been stored at a safe temperatureor has been spoiled at a higher temperature.

[0137] A chromic change agent may be incorporated into throat lozengesto tell the consumer that they have an elevated body temperature orfever. Alternatively, an aqueous form of the chromic material can beadded to a mouthwash, spray or gargle that changes color if the user hasa fever.

[0138] Alternative thermochromic materials: Alternative thermochromicmaterials that may have application as ingestibles include leucodyes,transition melting waxes, pigments that are released during hydration orshear, micro and nano-pigments, molybdenum, doped or undoped vanadiumdioxide, mercuric iodide, indolinospirochromenes, spiropyrans,polythiophenes, polybi-thiophenes, di-b-napthospiropyrans or the like.Alternative chromic change agents can be combined with food matricesusing methods described earlier. Methods for the preparation ofspiropyrans, including (Keum et al. (1995), Bull Korean Chem Soc 16:1007), polythiophenes (Lévesque et al. (1996) Chem Materials 8: 2843)and various other chromic change agents (Brown et al., eds., (1972)Photochromism, in Techniques of Chemistry, Vol. 3; Durr et al., eds.,(1990) Photochromism: Molecules and Systems (Studies in OrganicChemistry, 40)) have been described. All of these above references areincorporated herein by reference. Extensive modification orencapsulation may be required with compounds such as these to ensuresafe ingestion and consumption without toxic side effects.

[0139] Compounds such as spiropyrans and the like are of interest wherethe thermochromic change agent exhibits a color at one temperature anddisappears when the temperature is altered. Spiropyrans,polydiacetylenes and other related materials that change color or becometransparent can be used to reveal messages or graphics when overcoatedon a permanent pigment. Making messages appear or disappear is ofinterest to the food and entertainment industries for promotional,marketing, and sales programs.

[0140] Combinations of different chromic change agents: In some cases,multiple color changes may be desirable or required on some products.Different chromic change agents or classes of agents that change colorin response to different triggering mechanisms may be used on a singleproduct as distinct pH indicators, time temperature indicators,dissolved gas color indicators, ionic strength indicators, moistureindicating materials, chemical color change indicators, variousphotochromic materials, various thermochromic materials, variousmechanochromic materials, or the like. Combinations of polydiacetylenes,indolinospirochromenes, spiropyrans, polybithiophenes, leucodyes,di-β-napthospiropyrans, and other intrinsic color change agents, can beused alone or in combination. Combinations of these chromic changeagents can be accomplished by either co-mixing different agentshomogeneously or selectively placing the different chromic agents inzones so that each agent can be triggered by its designated triggeringmethod.

[0141] A variety of optical effects and applications can be envisionedby using multiple chromic change agents either specifically patterned orcoprocessed. For example, a series of chromic change agents can bepatterned by a dot matrix or offset printing process such that the zonesor images of one type of chromic agent can be visualized at ambienttemperatures or conditions. When the ambient temperatures or conditionsare altered, such as processes including cooking, heating, foodpreparation, eating or digestion, the patterns change in response toparticular triggering mechanisms. The chromic change patterns can bespecified or preprogrammed to achieve particular memory effects that canbe entertaining and/or informative. Entertaining pattern changes finduse in promotional applications such as a color change process thatleads the consumer stepwise through food purchasing, preparation andconsumption. Multipart color images or patterns and/or conditions whichchange in a complex or intricate manner may necessitate the use ofmultiple chromic change agents. Patterns that appear on ingestibles dueto the response of chromic change agents include text, characters,images, symbols, branding identities, messages, icons, logos, artisticdesigns or decorative designs.

[0142] Complex color patterns comprising multiple chromic change agentsmay be used to communicate directions or recipes to a potential oractual consumer. By way of example, a prepackaged food item mayincorporate a message on the item that suggests that the item bepurchased. After the package is opened, exposure to air, light or roomtemperature may cause the disappearance of the first message and asecond message such as “Now add substance A” to be displayed. Additionof substance A may induce a chemical change that leads to a chromicagent-induced pattern change and the next message, which may state, forexample, “Now bake at 350° F.”, “Add substance B”, or the like. Inaddition to text-based messages, an ingestible may be imprinted with aseries of graphical or “universal” displays that direct the consumer tothe next step. Examples of ingestibles that communicate directions mayinclude food items, pharmaceuticals or pills, or disposable swabs orother devices that require some degree of preparation by the preparer orconsumer.

[0143] Complex information pattern changes also find use in diagnosticsand sensing applications where the pattern change results when aningestible is consumed, digested and excreted, as described below.

[0144] Chromic change agents as diagnostic indicators: Intrinsic colorchange agents that are irreversible in color change can be used when itis important to preserve permanently or record a physiological process.Intrinsic color change agents that are reversible in color change can beused when it is important to record repeatedly a physiological eventand/or be able to trigger reversibly a chromic change agent to confirmhow it was originally recorded as a diagnostic mechanism.

[0145] The chromic change and substance release system can find use invarious ingestibles where it is desirable to indicate to an individualor health care worker that a drug, nutrient, over-the-counter medicineor the like has been appropriately released into the individual'sdigestive system. For example, a chewing gum or similar product that isretained in the mouth rather than swallowed, and that contains a chromicchange agent combined with a drug for delivery by chewing, can changecolor due the sheering forces of chewing or from reaction with salivarychemicals or enzymes. The chromic transition and corresponding colorchange serves as an indicator to the individual that the substance hasbeen fully released from the gum and that further chewing is no longernecessary in order to obtain the full effect of the substance.

[0146] A chromic change agent may be incorporated on an diagnosticingestible, such as a throat lozenge, which indicates the presence of apathogenic microorganism. Streptococcus pyogenes, the causative agent ofstreptococcal sore throat, is one such microorganism that may bedetected by this means. A chromic change agent may be associated withone of a binding pair such as an antibody, enzyme substrate, receptorligand, etc., that interacts directly or indirectly with themicroorganism or its products. For example, a chromic change agent maybe incorporated in the lozenge in a liposome or other lipid-basedcomposition that is modified by a lecithinase from the bacterium. Achromic change agent that interacts when it contacts salivary componentsor other bacterial metabolic processes or products could then changecolor upon release from the liposome. Alternatively, a chromic changeagent may be linked to one of a binding pair, and interaction with theother binding pair member causes a chemical change in the environment ofthe chromic change agent and a subsequent color change. An example wouldbe a chromic change agent bound to an enzyme substrate, wherein thesubstrate is specific for a particular microbial enzyme. The substratealters the pH or redox potential in the environment of the chromic agentwhen acted upon by the microbial enzyme, inducing a color change as aresult of a change in, for example, the ionization or redox potential ofthe chromic agent.

[0147] A diagnostic color change ingestible can be used by the medicalcommunity to evaluate a number of digestive tract disorders or bodilydysfunctions in vivo. Devices can be constructed with color changeagents in selective patterns alone or in combination where they areplaced on a carrier such as a pill-sized bead or the like, and thenconsumed. As the carrier is ingested and travels through the digestivetract, it encounters various points at which it can be triggered, andits color changes in a particular color-changing zone. As the digestiveprocess continues, the carrier can record the wellness or dysfunctionalstate of the digestive process. As the carrier is excreted during abowel movement it has a record of information of the digestive processand can be used to give the consumer or physician general or specificinformation about the digestive functionality in vivo. In order tofacilitate recovery and separation of the diagnostic color changeingestible from fecal matter, a separation means can be incorporatedinto the ingestible, such as, for example, a magnetic core.

[0148] Ingestibles incorporating chromic change agents may also find useas a detection method for bodily dysfunction such as ketosis or liverdysfunction resulting in the lack of ability to properly metabolizecertain food components. The resulting biochemical by-product in breathor saliva can act as a trigger for a color change in the chromic agent,the change indicating the presence of a bodily dysfunction. The chromicchange agent can be incorporated into a mouth wash, a gargle, a spray,or other convenient form that enables saliva or breath to come incontact with the chromic change agent and trigger a color change as anindication of a dysfunction.

EXAMPLES

[0149] Specific foods or other compositions that are taken orally thathave been or can be used with the subject invention, as illustrative ofingestibles generally.

[0150] Kellogg's Pop-tarts

[0151] Nabisco Cream of Wheat

[0152] Marshmallows

[0153] Kellogg's Rice Crispy Treats

[0154] Easy Bake Oven Products

[0155] Karo Syrup

[0156] Kellogg's Fruit Loops

[0157] Kraft Foods Jell-O

[0158] Hormel Franks Bologna

[0159] Pepperidge Farm Goldfish Soup Crackers

[0160] Nabisco Newtons

[0161] Flintstone Vitamins

[0162] Turns Antacid

[0163] Crest Toothpaste

[0164] Listerine Mouthwash

[0165] Throat lozenges

[0166] French toast sticks Burger King Cinnamon Buns Pillsbury frosting

[0167] Cinnamon Minis—Special dip frosting—Burger King

Example 1 Synthesis of Chromic Agents

[0168] Synthesis of N-ethanol-hexadeca-5,7-diyneamide: 1 molarequivalent 5,7-hexadecadiynoic acid (GFS Chemicals) was dissolved indichloromethane to a concentration of 100 mg/ml and stirred at roomtemperature. 1.05 equivalents of 1,1-dicyclohexyl carbodiimide (DCC)were added and the mixture stirred. An immediate white crystallineprecipitate formed indicating the presence of dicyclohexyl urea (DCU).The reaction mixture was stirred for 1 hour at room temperature.Ethanolamine (99.5% pure, Aldrich Chemicals) was added drop wise to theunfiltered stirring solution. The amide formation was checkedperiodically using TLC and spotting a filter paper then ultraviolet 254polymerization and testing reversible thermochromism (85° F. red/60° F.blue). The reaction was complete within 1 hour and left standing for atotal of 4 hours at room temperature. The DCU was filtered from thereaction mixture using gravity filtration (Whatman 541) and allowed tostand at 4° F. over night. Additional DCU crystals formed over night andwere filtered using gravity filtration (Whatman 541). The solvent andresidual ethanolamine was remove using a Rotovap. The reaction productwas resuspended in dichloromethane and refiltered using gravityfiltration (Whatman 541). The solvent was removed a second time using aRotovap. The reaction product was suspended in hexane/dichloromethanesolution (20/1 volume/volume). The suspension was warmed to near theboiling point of the solvent mixture to dissolve the product. Thereaction crystallization mixture was kept at room temperature for 6hours. The crystallized product was filtered using gravity filtration(Whatman 541), redissolved and recrystallized a second time.

[0169] N-ethanol-hexadeca-5,7-diyneamide can also be prepared by analternate synthetic route whereby the 5,7-Hexadecadlynoic acid can beconverted to an acid chloride and added directly to a stirring solutioncontaining ethanolamine to yield the final amide product. This route hasthe advantage of more direct purification since it eliminates the needto remove a coupling agent such as residual DCC or the DCU byproduct.

[0170] Synthesis of methyl 10,12-pentaeosadiynoate (MePDA):10,12-pentacosadiynoic acid (10 gm., GFS Chemicals) was dissolved in asolution containing 10 ml methanol (HPLC grade) and 10 ml chloroform(HPLC grade). The solution was stirred at room temperature and 10 dropsof neat sulfuric acid was added drop wise. The solution was warmed to100° F. for 2 hour. The reaction mixture was purified using columnchromatography. The product (MePDA) was dried using a Rotovap and thematerial stored in a chloroform solution. The solid form of MEPDA wasvery unstable to polymerization and therefore kept dissolved in organicsolutions.

[0171] Synthesis of methyl 10,12-tricosadiynoate (MeTDA):10,12-tricosadiynoic acid (10 gm., GFS Chemicals) was dissolved in asolution containing 10 ml methanol (HPLC grade) and 10 ml chloroform(HPLC grade). The solution was stirred at room temperature and 10 dropsof neat sulfuric acid was added drop wise. The solution was warmed to100° F. for 2 hour. The reaction mixture was purified using columnchromatography. The product (MeTDA) was dried using a Rotovap and thematerial stored in a chloroform solution. The solid form of MeTDA wasvery unstable to polymerization and therefore kept dissolved in organicsolutions. Alcoholic solutions of MePDA and MeTDA: Solids MePDA or MeTDAwere dissolved in reagent grade ethanol to a concentration of 150 mg/ml.A residual polymer was removed by filtration through Whatman No. 1filter paper. The solutions were held at room temperature or slightlyabove (70-75° F.) to avoid crystallization or precipitation.

[0172] Synthesis of dimethyl bis (10,12-pentacosadiynl oxyethyl)ammonium chloride (BRONCO): 10,12-Pentacosadiynoic acid (5 gm. 13.4mmol., GFS Chemicals) was dissolved in 60 ml dichloromethane andfiltered (Whatman No. 1) resulting in a colorless solution.1,3-Dicyclohexylcarbodiimide (3.6 gm, 17.5 mmol., Aldrich ChemicalCorp.) and the base 4-dimethylaminopyridine (one equivalent, AldrichChemical Corp.) were added to the solution and stirred for 15-20 minutesduring which time a white crystalline precipitate, dicyclohexylurea,formed. Bis(2-hydroxyethyl) dimethylammonium chloride (1.14 gm., 6.68mmol., Acros Organics-Fisher Scientific) was added to the reactionmixture and stirred over night in a dry inert atmosphere (nitrogen). Theurea precipitate was filtered out using (Whatman No. 1) and the reactionmixture was purified using column chromatography. Dimethylbis(10,12-pentacosadiynl oxyethyl) ammonium chloride, Bronco, was driedusing Rotovap and stored in a powder form.

[0173] Alcoholic Monomer Solution of TDA/PDA: 10,12-Tricosadiynoic acid(TDA, 6 gm GFS Chemicals) and 10,12-pentacosadiynoic acid (PDA, 0.9 gmGFS Chemicals) were dissolved in 60 ml ethanol (Fisher). The solutionwas slightly warmed and stirred. The solution (TDA/PDA) was filtered(Whatman No. 1) to remove residual polymer. Dye colorant could be addedto the alcoholic monomer solution as an indicator. Standard organicsolvent based dyes were added at 2 drops per ml.

Example 2 Preparation of Edible Printed Laminates

[0174] Ink Jet Printing: Black ink jet cartridges (Hewlett Packard 680Ccompatible or Cannon BJC2000) were modified to contain either theTDAIPDA or MePDA alcoholic monomer solutions. The cartridges were openedand the water based ink removed. The cartridges were flushed withethanol and the alcoholic monomer solutions added separately to eachcartridge. The cartridges were sealed, purged, and inserted into an inkjet printer (Hewlett Packard 680C or Canon BJC2000). Standard wordprocessing and graphics programs were utilized for printing. The ink jetcartridges were cleaned periodically to remove residual build up ofmonomer caused by drying.

[0175] Ink Jet Printed Thermochromic Sugar Laminates: Edible laminatesfor ink jet printing (Kopykake, Torrance, Calif.) were printed using theTDA/PDA or MePDA monomer solutions, food grade ink jet dyes, and the inkjet printing systems described above.

[0176] Air Brush Coating Surfaces: Alcoholic solutions contain TDA, PDA,TDA/PDA mixtures, or MePDA or an aqueous solution containing BRONCO wereprepared according to the methods described above and sprayed onto foodsurface using a standard hand held air brush Badger model 200, USA).Solutions were thinned or concentrated with their corresponding solventto achieve desired coating. Coating was accomplished by applying asteady stream of vaporized material to the surface at a distance of 1-6inches. Patterns were formed using paper stencils or by careful handmovement. After coatings were applied and allowed to dry, the surfaceswere polymerized using a hand held ultraviolet lamp (254 nm).

Example 3 Temperature Triggered Chromic Change Agents

[0177] 1. Temperature Indicating Ingestibles

[0178] 130-150° F. Thermochromic Corn Syrup: Temperature indicatingsyrup for hot pancakes, waffles, or the like were made using amicrocrystalline suspension of a polymeric polydiacetylene. 2 gm 10,12-tricosadiynoic acid was mixed with 45 ml corn syrup (Karo brand BestFoods, Englewood Cliffs, N.J.) and then probe sonicated at 40% powerusing a 400 watt sonicator (Cole Parmer Instruments, Vernon Hills, Ill.)for 5 minutes. The sample heated to about 140° F. during sonication.After uniform mixing, the sample was allowed to cool to room temperature(3 hours). A white cloudy suspension appeared within 1 hour. The samplewas mixed using a stir rod until a creamy consistency resulted. Thesample was polymerized to a deep dark blue color in a shallow plasticcontainer using a hand held ultraviolet lamp (254 nm, Cole ParmerInstruments, Vernon Hills, Ill.). The sample was irradiated for 4minutes and mixed using a stir rod.

[0179] The dark blue syrup was immediately available for use with hotfoods. The syrup could easily be spread on hot toast or waffles. Uponapplication to the food, the dark blue syrup turned bright red in colorindicating the surface temperature of the hot food it was applied to.The thermochromic transition temperature occurred at between 130° F. to150° F.

[0180] 110-130° F. Thermochromic Corn Syrup: Moderate temperaturetriggering corn syrup was made using the formulation described above andby adding absolute ethanol at 5% by volume. The ethanol was added to apremixed unpolymerized suspension. The suspension and ethanol were mixedto uniformity for 5 minutes at room temperature and polymerized usingthe identical conditions described above. The thermochromic transitiontemperature of the polymerized mixture occurred at between 110° F. to130° F.

[0181] Temperature Indicating Thermochromic Icing/Syrup: 5 ml of theMePDA alcohol solution (above) and 10 gm cake icing (Signature Brands,LLC, Ocala, Fla.) were uniformly mixed at room temperature for 10minutes. Most of the ethanol from the solution evaporated. The resultingcreamy paste was chilled to below freezing (−10° F.) and then exposed toan ultraviolet lamp (hand held, 254 nm) for 5-10 minutes while remainingchilled. The mixture was churned during exposure to give a uniform blueappearance. The thermochromic icing was temperature triggered by simplyraising it above freezing (greater than 50° F.). The icing immediatelyturned bright red when applied to surfaces exposed to room temperature,directly exposed to room temperature, or touched by directly by hand.Oils contained within the icing helped to facilitate the temperaturetriggering of the thermochromic agent in the icing. Partiallyhydrogenated vegetable oils (soybean and cottonseed) are solid in natureat freezing temperatures, keeping the blue polymeric MePDA stable. Asthe oils melt at above room temperature, the polymeric MePDA issubsequently influenced to transition from a dark blue color to a brightred. The icing was further packaged in air sealed plastic pouches (4mil, polyethylene) and heat-sealed using a conventional heat sealer.Care was taken not to expose or contact the dark blue frosting totemperatures above freezing. The frosting/syrup could conveniently beextruded onto a pastry surface. During the application, the dark bluecolor turned immediately bright red due to finger contact with the pouchand exposure to a room temperature surface.

[0182] Low Temperature Indicating Marshmallows: Marshmallows werequickly dip coated into the MePDA alcohol solution and allowed to dry atroom temperature or below. The monomer dip coated marshmallows wereexposed to ultraviolet light (hand held lamp, 254 nm) and rotated foruniform polymerization (approximately 2 minutes) until they became darkblue. The marshmallows were stable at room temperature or below (68°F.). They immediately changed to a bright red/orange color upon directtouching, contact with warm fluids, or placing in the presence of anopen flame (95° F. or above).

[0183] High Temperature-indicating Hot Chocolate: Yellow dye number 6,red dye number 40, and a medium blue polydiacetylenic thermochromicagent that turns orange when triggered by heating were added to a hotchocolate mix prepared at room temperature. The resulting combination ofhot chocolate, dyes and thermochromic agent was brown in color. When hotwater was added to the solution, the brown color changed to acombination of yellow and red, bringing the brown mix to a bright orangecolor.

[0184] 2. Cooking State-Indicating Ingestibles

[0185] Temperature Indicating Frozen Waffles: Frozen waffles (Eggobrand, Kellogg Company) were removed from their package and immediatelysprayed with an alcohol based monomer solution (above). Waffles werecoated at 68° F. using a standard airbrush. Patterns were created usingthe square cells on each waffle. The monomer solution dried immediatelyon the waffle surface. The monomer-coated waffles were polymerized usinga hand held ultraviolet lamp (254. nm, 6 inches for 10 to 60 seconds).Radial polymerization gradients were used to increase the level ofpolymerization from the outer region of the waffle to the center.Increasing the level of polymerization causes a corresponding increasein the final colorimetric temperature transition of the thermochromicagent. The resulting waffles had a dark blue appearance uponpolymerization. The patterned thermochromic indicating waffles wereconveniently re-stored in the freezer prior to use. The temperatureindicating waffles were toasted using normal instructions on thepackage. As the waffles were heated, the dark blue color changed to abright red/orange. The outer portions of dark blue changed color first.As heating continued, the inner portions of blue at the center of thewaffles turned color to red/orange last. The color transition wascomplete when the waffles were fully heated indicating that toasting wascomplete and the waffles ready to serve.

[0186] Ground meat patty possessing a chromic change agent particle forindicating internal safe cooking temperatures: Chromic change particleswere prepared by coating sesame seeds with a thin layer of a chromicchange agent. An ethanol solution was prepared with ethanol (SpectrumChemicals, Inc.) containing 150 mg/ml 10,12-tricosadiynoic acid and 15mg/ml 10,12 pentacosadiynoic acid. The solution was warmed to 100° F. todissolve all of the diacetylenic acid. 10 gm sesame seeds were placed ina screw cap vial and saturated with 2 ml of ethanolic solution. Theseeds and solution were shaken and tumbled for 3 minutes to ensurecomplete coverage of each seed. The seeds were poured into a Tefloncoated dish and tumbled for 10 minutes with a gentle air stream toensure that all of the ethanol solution was removed. The coatedparticles were vigorously shaken and exposed to ultraviolet light (handheld lamp, Cole Parmer, Inc. 254 nm) for 5 minutes resulting in the deepblue appearance of the polydiacetylenic polymer. The coated particleswere stored overnight at room temperature.

[0187] The blue polymer coated particles were admixed with groundhamburger meat to a concentration where multiple particles were presentin the central region of a patty each time a patty was sliced throughPatties was grilled on a gas grill and flipped over during cooking. Thecenter of patties were systematically tested during grilling todetermine the extent of color change during cooking. Color changeparticles toward the outer segments of a patty turned color to a brightred/orange earliest during cooking. Color change particles in the centerof a burger turned color to a bright red/orange once the burger'sinternal temperature achieved 160° F. indicating that the burger wascooked thoroughly.

[0188] Baby Food: The likelihood that a child will be burned byingesting overly-heated baby food solids and liquids may besignificantly reduced by using a color reversible thermochromic agentcombined with a food or formula. Solid foods or formulae may be preparedwith a blue thermochromic agent. Upon heating the food or formula thethermochromic agent changes color to orange, indicating a hightemperature, which then reverts to the blue color when the temperatureof the food or formula is safe to ingest. The thermochromic agent canalso be used to indicate uneven temperature distribution in variousregions of the food or formula, and that the food should be mixed toachieve a more uniform, safe temperature.

[0189] Thermochromic Graphically Patterned PopTarts: PopTarts (KelloggCompany) were coated with a commercially available sugar glaze andallowed to dry for several hours at room temperature. Edible laminatesjet printed (Kopykake, Torrance, Calif.) with either TDAIPDA or MePDAmonomer solutions and the Kopyjet ink jet printing system as describedabove were applied to the glazed PopTart surface. Initially the glazesurfaces were slightly wetted to facilitate the adherence of the ediblelaminate. Various entertaining patterns were graphically rendered forapplication on the PopTarts. The monomer printed surfaces werepolymerized using a hand held ultraviolet lamp (254 nm) at a distance of3 inches for 5 to 10 seconds depending on the desired level of bluecolor. TDA/PDA printed/polymerized PopTarts changed color from a darkblue to a bright red/orange when exposed to toaster or microwavetemperatures. MePDA printed/polymerized PopTarts changed color from adark blue to a bright red/orange when exposed to finger touch or above90° F.

[0190] Franks and Hot Dogs: Processed hot dogs can be impregnated with athermochromic material which turns color when a specific heat isachieved. The material can be patterned such that lettering may indicatethe words “HOT DOG” for promotional and advertisement value.Conveniently, an aqueous form of the thermochromic agent is ink jetprinted into a pattern representing words of interest. The polymerizabledual chain lipid BRONCO was suspended in water and pre-polymerize withultraviolet light (254 nm) at room temperature to a dark blue ink color.The polymer solution was printed on the side of a retail available hotdog (Hormel or Kraft). The chromic agent can also be printed on the meatproduct cellulosic casing prior to filling the casing with processedmeats and fillers. Casings are typically extruded, processed, and driedprior to filling. Printing on the unfilled casing provides the advantageof printing on a dry solid surface using high speed printing and dryingmethods with out effecting the foodstuff. Printing on the casing caninvolve ink jet printing, pad printing, masking, spraying, silkscreening, extrusion or the like.

[0191] Brownie Mix: Brownie mixes were prepared by incorporating a bluethermochromic agent that changes to bright orange upon heating. Uponpreparation of the brownie mix according to the manufacturer'sdirections and baking, the dark brown mix became bright orange. Thethermochromic agent thus served as both an entertaining color changecomponent of the mix, and as an indicator that the brownies were doneand ready to be removed from the oven.

[0192] Embedded food bar codes: Embedded thermochromic bar codesproduced directly on the side of a pre-baked ham cut. A thermochromicbar code allows a standard bar code and bare code reader to be used as athermometer device. An alcoholic solution containing TDAIPDA (describedabove) was sprayed locally on the side of a 1 pound piece of pre-cookedham (Hormel Company). The ham surface was prepared by damp drying a 1×2inch region. The region was sprayed at a distance of 3 inches using anairbrush as described above. An ultraviolet transmissive photomask witha negative bar code pattern was prepared using a black film thermaltransfer printer (Brother) and 8.5×11 inch sheet of 4 mil thick clearpolyethylene sheet. The bar code photomask, sized to 0.75 by 1.5 inch,was placed directly over the sprayed region of TDA/PDA. The bars in thecode were transmissive to ultraviolet light (254 nm). The bars wereselectively exposed using a light shield over certain bars while otherswere exposed. This method allowed some bars to be polymerized for 100%more time than others did so that the lesser exposed bars would changecolor at lower temperatures (125° F.) and the more highly exposed barswould change color at higher temperatures (170° F.). The differentialtemperatures were set so that a bar code reader could read while ham washot so that the bar code scanner could interpret the disappearance ofcertain bars (due to the dark blue to red color transition duringheating) as being a different code than when it started. The scannerinformation was converted digitally using a standard computer so thatthe corresponding computer output could indicate the actual temperature.

[0193] 3. Decoration of Ingestibles

[0194] Thermochromic cereals: A low temperature reversible thermochromecan be prepared in a versatile polyethylene glycol coating. A coatingsolution containing the polymerizable monomerN-ethanol-hexadeca-5,7-diyneamide (100 mg/ml) 3,350 molecular weightpolyethylene glycol (750 mg/ml) was made in an ethanol (absolute) bywarming to 120° F. and mixing. The viscous solution remained clear above100° F. The coating solution is slightly viscous and easily applied to afood surface by blotting, painting, or spraying. Both theN-ethanol-hexadeca-5,7-diyneamide and polyethylene glycol crystallizefrom solution upon cooling to room temperature and solvent evaporation.Foods cereals such as Kellogg's Frosted Miniwheats were coated bypainting with a thin coat and allowed to dry at room temperature for 2hours. The resulting coat dried to a hard wax-like appearance. TheN-ethanolhexadeca-5,7-diyneamide was polymerized using a hand-heldultraviolet lamp (254 nm, 6 inch distance) for a total exposure time of1 minute. The resulting layer became strongly magenta at roomtemperature 68 72° F.), bright red/orange at increasing temperature(85-95° F.), and dark blue/purple when chilled (35-55° F.). The colorchange is completely reversible as long as the upper temperature levelis maintained below 130° F. The coated cereal pieces turn from a brightmagenta/red to dark purple/blue when cold milk is poured over theirsurface (42° F.). The dark purple/blue color remains as long as the milkremains cold. The color is thermochromically reversible through hot andcold cycles.

[0195] Processed thin sliced cheese: Pre-packaged thin sliced cheese canbe printed with the aqueous solution of the thermochromic agent. Thesolution can be pre-polymerized or in a monomeric form which can bepolymerized after printing. The thermochromic agent is absorbed to thecheese surface upon brief drying causing a strong bonding to occurbetween the thermochromic agent and the surface of the cheese.

[0196] A pattern of the American flag was produced on the surface of athin slice of American cheese (Kraft 2% Milk Reduced Fat Milk Singles).The pattern was painted using a thin brush and a dark blue solution ofpre-polymerized BRONCO. The pattern was allowed to dry at roomtemperature for 5 minutes and the cheese repackaged for storage.

[0197] The flag-painted slice of cheese was placed on a hamburger whilethe burger was cooking on a grill. Within 2-3 minutes, the cheese beganto melt. During heating and melting, the dark blue flag pattern becamebright red. The flag pattern also started to flow and contort as thecheese melted and flowed. The flow process gave rise to an interestingeffect, simulating a waving and moving flag.

[0198] Thermochromic sugars, salts, spices, cheese powders, gratedcheese, and shredded cheese: An ethanol coating solution was preparedwith ethanol (Spectrum Chemicals Inc.) containing 150 mg/ml10,12-tricosadiynoic acid (GFS Chemicals, Inc.). The solution was warmedto 100° F. to dissolve all of the diacetylenic acid. Twenty grams ofsugar, salt, spice (e.g. paprika or mustard seeds), or cheese powder(e.g. Parmesan cheese or powdered cheese from Kraft Macaroni and Cheesemix) were added to a screw cap bottle and saturated with up to 2.5 ml ofthe ethanolic solution. A powder and solution were shaken and tumbledfor 3 minutes to ensure complete coverage of the particles. The solutionwetted powders were poured into a Teflon coated dish and tumbled for 10minutes with a gentle air stream to ensure that all of the ethanolsolution was removed. The coated powders were vigorously shaken andexposed to ultraviolet light (hand held lamp, Cole Parmer, Inc. 254 nm)for 5 minutes resulting in the deep blue appearance of thepolydiacetylenic polymer. Once dry, the coated powders could be usedimmediately.

[0199] Thermochromic triggering was accomplished by applying a powdertype directly to a heated food type. For example, the chromic agentcoated powder cheese was added to a pre-heated/cooked bowl of macaroni.On contact, the dark blue cheese powder turns to a vivid red orangecolor. Visual effects can be created by first adding a small pile of thetreated pile to a hot food. At first the shallow edges turn orange andthen the blue pile gradually turns orange with the orange colorradiating inward until finally the peak is triggered orange.Alternatively, the coated powder can be sparsely sprinkled on the foodsuch that each grain turns color instantly.

[0200] Thermochromic soup crackers: Soup crackers (e.g., PepperidgeFarms Fish Cracker brand or standard soup crackers) were lightly sprayedand wetted with an adhesive food glaze (150 mg/ml water soluble starchdissolved in purified water sprayed with a nebulizer). The lightlywetted surface was tacky to the touch for several minutes prior todrying. While the surface was tacky, the crackers were coated with athermochromic salt powder as prepare above. The coated salt particlesadhered to the cracker surface once the adhesive food glaze dried. Thefinal crackers revealed a blue tint on their surface. The opticaldensity of blue color was regulated by the amount of coated saltapplied.

[0201] Thermochromic triggering was accomplished by dipping a crackerinto a hot bowl of soup. The dark blue tint on the cracker surfaceturned immediately to a bright orange on contact with the hot liquid.Visual effects were created by dipping the crackers at various depthsand angles into the soup.

[0202] 4. Storage Temperature Condition Indicators

[0203] Raw egg holding temperature indicator: Eggs were printed with thealcoholic solution containing MeTDA described above. The monomersolution was spot printed using a porous felt pad saturated with themonomer solution. Printing was conducted while the eggs were held at 40°F. The monomer was allowed to dry for 2 minutes and polymerized at usinga hand held ultraviolet lamp (254 nm) at 40° F. The dark blue printedspot held its color on an egg until the egg was raised to between 55 to65° F. were the dark blue spot became bright red/orange indicate thatthe egg was exposed to an excessive holding temperature range. Eggsshould be kept at refrigerator temperature during storage due to thepotential contamination of Salmonella and the possibility of cellreplication at above refrigerator temperatures.

Example 4 Mechanical Stress-Triggered Chromic Change Agents

[0204] Candies and cookies possessing mechanically induced colorchanges: Hard candies such as jaw breakers, M & M's, hard coated gumpieces, hard icing coated cookies, or the like were coated with a colorchange agent that changes color due to mechanical and/or frictionalforces applied to the surface with the mechanochromic agent. An ethanolcoating solution was prepared with ethanol (Spectrum Chemicals, Inc.)containing 200 mg/ml 10,12-octadecadlynoic acid (GFS Chemicals, Inc.).The solution was spray coated onto candy or cookie surfaces using aconventional air brush system. The coating can be applied either whilethe candy or cookie surface is stationary or tumbling. Once an even coathas been applied, the surfaces are allowed to dry at room temperature of30 minutes. The coated surfaces are polymerized using an ultravioletlight (hand held lamp, Cole Parmer Inc. 254 nm) for 5 minutes resultingin the blue appearance of the polydiacetylenic polymer.

[0205] Candy and cookie surfaces coated with the blue polydiacetylenelayer are changed to a red/orange color by rubbing surfaces together,rubbing with a finger or finger nail, or rubbing with a compatible hardsurface. Surfaces with temperature insulative properties such as fingernails, napkins, wood sticks, paper dowels, plastic sticks or the likeare superior for inducing the color change compared with metal or glasssurfaces which have heat conductive surfaces. Patterns, messages, andgraphical images can be created on the mechanochromic surface bylocalized rubbing without changing the color of an adjacent region ofthe blue mechanochromic agent.

[0206] Mechanochromic tooth paste: A ratio of 10 g Crest Tooth Pastewith 1 gram pre-polymerize flakes of 5,7-hexadecadiynoic was mixed atroom temperature to become a blue paste containing small blue particlesof the diacetylenic polymer. 5,7-hexadecadiynoic acid (GFS Chemicals,Inc.) flake-like crystals were polymerized to a dark blue tint using ahand-held ultraviolet lamp (Cole Parmer inc.) for 3 minutes. The flakeswere agitated during the process to ensure complete polymerization. Thedark blue flakes were added to tooth paste at room temperature and mixedthoroughly. The final formulation was stable at room temperature. Themechanochromic tooth paste turned form a dark blue paste to apink/purple color when the tooth paste was abraded back and forth with astandard tooth brush (medium bristles) for 2-3 minutes.

[0207] Touch Sensitive Rice Krispie® Treats: Retail Rice Krispie Treats(Kellogg Company) were air brush spray coated using the method describedabove and an alcoholic solution of MePDA prepared as described above.The Rice Krispie Treats surfaces were inclined at 30 degrees on an opentray and sprayed at a distance of 4 inches using a moderate stream flowfrom the airbrush. The coatings were allowed to dry for 5 minutes at 65g. Pattern coating was accomplished using an open letter stencil andspraying just beyond the outline of the stencil. Polymerization wasaccomplished using a hand held ultraviolet lamp (254 nm) moved back andforth over the surface for 5 seconds at a distance of 3 inches. Thesurface immediately became dark blue and could be made to change colorto a bright red/orange by finger touch, breathing on the surface, orbiting into the surface.

Example 5 Combined Temperature-Mechanical Stress-Triggered ChromicChange Agents

[0208] Combined photochromic thermochromic-mechanochromic cookies: Anethanol solution was prepared with ethanol (Spectrum Chemicals, Inc.)containing 150 mg/ml 10,12-tricosadiynoic acid and 15 mg/ml10,12-pentacosadiynoic acid. The solution was warmed to 100° F. todissolve all of the diacetylenic acid. The solution was loaded into anemptied, cleaned, and dried ink jet cartridge (Hewlett Packard HP51629A). The cartridge was placed in an ink jet printer (HewlettPackard, Deskwriter 680C). The printing room and printing componentswere maintained at a temperature of 95° F. to ensure that the ethanolprinting solution remained soluble. Edible laminates (Kopykake Inc.,Torrance, Calif.) were printed using standard graphics programs andinterfaces.

[0209] Graphical images were printed on the laminate and then adhered tothe surface of cookies. The cookies were place in the sun or exposed toa hand held ultraviolet light source (Cole Parmer, Inc.). The graphicalimages appeared exactly as they were printed upon exposure. Thegraphical images became visible within minutes in sun light (peakintensity at 12:00 noon during the spring time in California). The colorbecame progressively darker with continued exposure up to hours.

[0210] The dark blue images printed on the cookies could be subsequentlytriggered to a bright red upon heating the cookie or dipping it in hotliquid (milk heated to 130° F.). Variations ultraviolet activated colordevelopment times and thermochromic temperature transitions can beachieved by modifying the polydiacetylene structure utilized.

[0211] The blue polydiacetylenic images on the cookie surface can alsoundergo a mechanochromic transition to a red/orange color by mildlyrubbing the image/cookie surface. The mechanochromic effect is highlylocalized to the specific are being contacted. The image can begraphically altered by localized rubbing to achieve different graphicaleffects based on multiple colors (e.g. the background cookie color, theblue form of the polymer, and the red/orange form of the polymer).

Example 6 Combined Temperature-Chemical Triggered Chromic Change Agents

[0212] Chromic change liquid beverage with dual function: An aqueoussuspension 100 mg/ml of N-ethanol-hexadeca-5,7-diyneamide was preparedusing ultrasonication and lecithin as an emulsifier. One gramN-ethanol-hexadeca-5,7-diyneamide (prepared as described in this patent)and 1 gram egg lecithin (Sigma Chemicals, Inc.) were added to a glassbeaker along with 30 ml filtered water and sonicated with a high powerprobe sonicator (Cole Parmer, Inc.) for 10 minutes at 130° F.Homogeneous suspension formation required agitation and mixing. Thefinal suspension was milky white. The suspension was allowed to cool toroom temperature and left to stand 24 hours. The suspension wasdispersed by mixing or agitation. Five ml of the solution was added to ashallow dish and exposed to ultraviolet light (hand held lamp, ColeParmer, Inc. 254 nm) for 5 minutes (with continual mixing and agitation)resulting in the deep magenta appearance of the polydiacetylenic polymer(room temperature). The magenta color chromic solution could be dilutedwith water or kept concentrated.

[0213] For thermochromic conversion, a 5 fold diluted solution of thechromic solution (purified water) was poured over crushed ice in a clearglass. The color immediately changed to a dark purple/blue color uponchilling. The solution color was thermochromically reversible whenrewarmed to room temperature and subsequently chilled back to nearfreezing temperatures. Temperature cycling could be repeated numeroustimes.

[0214] For chemochromic conversion the chilled purple/blue chromicsolution can be further changed to a bright pink/orange color by theaddition of alcohol (chilled or ambient in temperature). Addition of anincreasing concentration of alcohol caused the purple/blue color toprogressively turn irreversibly to a pink/orange color. When greaterthan 50% alcohol (volume/volume water/alcohol) is added the solutionbecomes completely pink/orange. The system serves as a means to detectthe presence of polar solvents such as alcohol or acetone.

Example 7 Moisture Triggered Chromic Change Agents

[0215] Hydrochromic ingestible sugar, sprinkles, nonpareil and saltpowders: An ethanol coating solution was prepared with ethanol (SpectrumChemicals, Inc.) containing 130 mg/ml 4,6-decadiyne-1,10-diol (GFSChemicals, inc.). 20 grams sugar or salt powder were added to a screwcap bottle and saturated with up to 2.5 ml of the ethanolic solution. Apowder and solution were shaken and tumbled for 5 minutes to ensurecomplete coverage of the particles. The solution wetted powders werepoured into a Teflon coated dish and tumbled for 10 minutes with agentle air stream to ensure that all of the ethanol solution was removedand the coated powder consisted of a in a fine grain mesh with outclumps. The coated powders were vigorously shaken and exposed toultraviolet light (hand held lamp, Cole Parmer, inc. 254 nm) for 5minutes resulting in the deep blue/purple appearance of thepolydiacetylenic polymer. Once polymerized the coated powders could beused immediately. Hydrochromic powders were stored at room temperatureof below in sealed jars and desiccants.

[0216] Hydrochromic powders were adhered to food surfaces such ascereals, cookies, crackers or any other food type intended to come incontact with an aqueous medium. For example, a hydrochromic sugar can becoated on the surface of a cookie intended of dipping in milk. Thevisual appearance of the blue/purple sugar powder can be enhanced bypre-coating the cookie with a bright white royal hard sugar icing.Immediately prior to the final drying stage of icing, a hydrochromicsugar powder can be layered on to the icing surface. Residual water inthe cookie icing will not change the outward surface color of thehydrochromic sugar powder as long as the water content in the icing isminimized and the grains do not wet. A gentle air stream over thecoating facilitates drying. Alternatively a tacky adhering glaze can beused for coating the food surface with the powder. The blue/purplepowder can be coated at a density practical for viewing.

[0217] Hydrochromic triggering is accomplished by dipping a coatedcookie into chilled milk (liquid at room temperature or as low as 45°F.). The blue/purple color changes to a bright orange on wetting. Thecolor change within seconds using liquids at near room temperature andhas a delayed effect over 30 to 90 seconds using liquids well below roomtemperature (45° F. to 55° F.).

[0218] Powders with very thin coats of the hydrochromic agent changecolor more rapidly than coatings that are thick since thicker coatingsare restrictive in letting water rapidly intercalate into the chromicagent's interstitial layer. The visual effect of hydrochromic colorchange can be regulated depending on the food type of interest.Hydrochromic coatings can also find use as integrated indicators thatfoods have been properly sealed form moisture there by ensuringfreshness and dryness during storage.

[0219] It is evident from the above description and results that byusing a thermochromic agent that undergoes a color change, manyapplications accrue. The thermochromic agent may be applied to a widevariety of ingestibles in a wide variety of manners, incorporated intothe ingestible, particularly liquids, or associated with the ingestible,such as on packaging materials. The thermochromic composition can beused to ensure that an ingestible has been stored safely, that it hasbeen cooked to a desirable temperature, that it has cooled to a desiredtemperature, or solely for marketing or entertainment purposes. Exposureof ingestibles comprising moisture-sensitive chromic change agents tosolutions or moist atmospheres can provide entertaining color changes orreveal text or imaged based messages. Mechanical stress-triggeredchromic change agents that change color due to mechanical and/orfrictional force may be incorporated into a variety of ingestibles thatare rubbed, scratched, chewed, compressed, or the like, and findparticular use in toothpastes and touch-sensitive ingestibles.Ingestibles incorporating a number of different chromic change agentcombinations are provided that can reveal different text messages orimages and sequentially-displayed text or images based on the types oftreatments to which the ingestible is exposed. These messages may serveto direct the user to the next step in a preparation process, revealhidden messages, and serve as diagnostic indicators. The compositionsare physiologically safe and may be modified to be appropriate as to aparticular temperature transition and compatible with the ingestible.

[0220] All publications and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication or patent application was specificallyand individually indicated to be incorporated by reference.

[0221] The invention now being fully described, it will be apparent toone of ordinary skill in the art that many changes and modifications canbe made thereto without departing from the spirit or scope of theappended claims.

What is claimed is:
 1. A method for effecting at least one color changein or on an ingestible, comprising; incorporating into or onto saidingestible a diacetylenic compound that undergoes said at least onecolor change when subjected to at least one environmental change; andsubjecting said ingestible to said at least one environmental change,whereby said at least one environmental change triggers said at leastone color change on said ingestible.
 2. The method according to claim 1,in which said at least one environmental change is selected from thegroup consisting of change in temperature, pH, illumination, chemicalexposure, biochemical exposure, mechanical stress, ionization,protonation, hydrogen bonding, state of hydration, and state ofsalvation.
 3. The method according to claim 1, wherein said ingestiblecomprises a food, medicament or swab.
 4. The method according to claim1, wherein said at least one color change forms at least one pattern onsaid ingestible.
 5. The method according to claim 4, wherein said atleast one pattern is selected from the group consisting of text,characters, images, symbols, branding identities, trademarks, messages,icons, logos, artistic designs and decorative designs.
 6. The methodaccording to claim 5, wherein said at least one pattern is changedsequentially in time-resolved text or images.
 7. A method for effectingone or more color changes on a packaging material or container forholding an ingestible, comprising; incorporating into or onto saidpackaging material or container a diacetylenic compound that undergoes acolor change when subjected to at least one environmental changeselected from the group consisting of change in temperature, pH,illumination, chemical or biochemical exposure, mechanical stresses,ionization, protonation, hydrogen bonding, state of hydration orsolvation; and subjecting said packaging material or container to saidat least one environmental change.
 8. A method for detecting whether aningestible has been exposed to an absolute temperature level, saidmethod comprising: associating with said ingestible a diacetyleniccompound that undergoes an irreversible color change when subjected to achange in temperature, wherein a color change associated with saidingestible is indicative that said ingestible has been exposed to saidabsolute temperature level.
 9. The method according to claim 8, whereinsaid diacetylenic compound is attached to a container or packagingmaterial for ingestibles.
 10. The method according to claim 8, whereinsaid color change indicates said ingestible has been spoiled.
 11. Themethod according to claim 8, wherein said color change indicates saidingestible is cooked.
 12. A method for indicating a temperature of aningestible, said method comprising: incorporating a diacetyleniccompound that undergoes a reversible color change when subjected to achange in temperature in or on said ingestible or an ingestiblecontainer, whereby color of said diacetylenic compound is indicative ofsaid temperature when said color is observed.
 13. A method for detectingwhether an ingestible has been exposed to moisture, said methodcomprising: associating with said ingestible a diacetylenic compoundthat undergoes an irreversible color change when subjected to moisture,wherein a color change associated with said ingestible is indicativethat said ingestible has been exposed to said moisture.
 14. A method fordetecting whether an ingestible has achieved a safe cooking level andhas cooled to a temperature that is safe to eat, said method comprising:associating with said ingestible a diacetylenic compound that undergoesan irreversible color change when subjected to a safe cookingtemperature and a reversible color change when said diacetyleniccompound reaches said temperature that is safe to eat, wherein saidirreversible color change is indicative that said ingestible hasachieved said safe cooking level and said reversible color change isindicative that said ingestible has reached said temperature that issafe to eat.
 15. A method for indicating elevated body temperature in amammal, comprising: administering to said mammal an ingestiblecomprising a diacetylenic compound, wherein said diacetylenic compoundundergoes a color change at a temperature above normal body temperatureof said mammal; and observing said ingestible for said color change,wherein said a color change is indicative of an elevated bodytemperature.
 16. The method according to claim 15, wherein saidingestible is a lozenge, pill, tablet, probe, mouthwash or gargle.
 17. Amethod for protecting a food comprising a diacetylene compound frompremature color change, said method comprising: associating with saidingestible a diacetylenic compound that reversibly changes color whensubjected to a change in temperature, and irreversibly changes colorwhen subjected to a different environmental change.
 18. The methodaccording to claim 17, wherein said food is a cereal and said differentenvironmental change is exposure to a liquid.
 19. A method of applying apattern on a surface of an ingestible, wherein said method comprises:applying a diacetylenic compound in varying concentrations to aningestible or ingestible container, whereby a local level ofpolymerization of said diacetylenic compound is used to create achanging graphic throughout a temperature triggering process.
 20. Amethod for manufacturing an ingestible comprising a diacetyleniccompound, wherein said method comprises: applying said diacetyleniccompound by ink jet printing, dot matrix printing, offset printing, padprinting, extrusion, spraying, use of liquid applicators, dip coating,sublimation, spreading, dripping, dye sublimation printing, or byapplication of laminates or edible labels.
 21. A method formanufacturing an ingestible comprising a diacetylenic compound, saidmethod comprising applying said diacetylenic compound in a compositionof up to 75% weight % of a diacetylenic compound.
 22. The methodaccording to claim 21, whereby said composition is up to about 60%weight % of a diacetylenic compound.
 23. The method according to claim21, whereby said composition of up to about 20% weight % of adiacetylenic compound.
 24. The method according to claim 21, whereinsaid diacetylenic compound is a lipid mono- or dicarboxylic non-oxocarbonyl monomer, or derivative thereof. 25.N-ethanol-hexadeca-5,7-diyneamide, or derivatives thereof.
 26. Adiacetylenic compound that undergoes a change color one or more times inresponse to a change in temperature comprisingN-propylamine-eicosa-5,7-diyneamide, or derivatives thereof.
 27. A solidmaterial in contact with food comprising a diacetylenic compound havinga transition temperature in a range of about −10 to 200° C.
 28. Thesolid material according to claim 27, wherein said solid material is apackaging material or food container.